Charged Particle and Photon Interactions

Charged Particle and Photon
Interactions with Matter

C he mi c a I, Physic oc h emi c a I, a nd B iolog i ca I
Consequences with Applications
edited by
A. Mozurnder
University of Notre Dame
Notre Dame, Indiana, USA .
Y. Hatano
Tokyo Institute of Technology
Tokyo, Japan
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Preface
The purpose of this work is to present a coherent account of high-energy charged particle
and photon interactions with matter, in vivo and in vitro, that will be of use to both students
and practicing scientists and engineers. The book encompasses not only radiation chemis-
try and photochemistry, but also other aspects of charged particle and photon interactions,
such as radiation physics, radiation biochemistry, radiation biology, and applications to
medical and engineering sciences and to radiation synthesis and processing and food
irradiation. Any phenomenon of ionization and excitation induced by charged particle
and photon interactions with matter is considered of interest, since information on the
interactions of photons with matter help us understand the interactions of charged particles
with matter. Further, the study of the interactions of high-energy photons, particularly in
the vacuum ultravioletsoft X-ray (VUV-SX) region, is of great importance in bridging the
area between photochemistry and radiation chemistry (see Chapter 5). Throughout the
book a major aim has been to elucidate the physical and chemical principles involved in
applications of signicance to practicing scientists and engineers. We have secured the
foremost workers in their respective areas to contribute chapter articles in a manner that
ensures contact with adjacent disciplines, keeping in mind the needs of the general reader-
ship.
Since its inception, radiation eects have had ramications in various elds, which
sometimes use dierent technical language, units, etc. Reviews condense the subject matter
while amplifying important points and bring these up-to-date for students and researchers.
In a eld that is developing as rapidly as radiation eects in vivo and in vitro, there is a need
for periodic summaries in the form of a book. In the present millenium, a great need has
developed for in-depth studies with a balance of experiment, theory, and application. Yet,
chapters written by several authors in the same book may use dierent styles, outlooks, or
even notations. We have paid particular attention to these factors and have striven to make
the presentations uniform.
By its very nature this book is interdisciplinary. The rst eleven chapters delineate the
fundamentals of radiation physics and radiation chemistry that are common to all irra-
diation eects. Chapters 12 and 13 deal with specic liquid systems, while Chapter 14 is
concerned with LETeects. Chapters 15 to 18 describe biological and medical consequences
of photon and charged-particle irradiation. The rest of the book is much more applied in
character, starting with irradiated polymers in Chapter 19 and ending with applications of
heavy ion impact in Chapter 27.
Our aim has been to provide a self-contained volume with sucient information and
discussion to take the reader to the frontier of investigation. The level of presentation is at
the advanced undergraduate level, so that undergraduates, graduate students, researchers,
and practicing professionals may all benet from it. It is assumed that the reader has some
knowledge of chemistry or biology or physics but is not necessarily versed in the properties
of high-energy radiation.
It is our pleasure and privilege to thank our friends and colleagues all over the world
who have contributed to our understanding of the high-energy charged particle and photon
interactions with matter.
A. Mozumder
Y. Hatano
Contents
Preface
Chapter 1 Introduction
A. Mozumder and Y. Hatano
Chapter 2 Interaction of Fast Charged Particles with Matter
A. Mozumder
Chapter 3 Ionization and Secondary Electron Production by Fast
Charged Particles
Larry H. Toburen
Chapter 4 Modeling of Physicochemical and Chemical Processes
in the Interactions of Fast Charged Particles with Matter
Simon M. Pimblott and A. Mozumder
Chapter 5 Interaction of Photons with Molecules: Photoabsorption,
Photoionization, and Photodissociation Cross Sections
Noriyuki Kouchi and Y. Hatano
Chapter 6 Reactions of Low-Energy Electrons, Ions, Excited Atoms
and Molecules, and Free Radicals in the Gas Phase as Studied by
Pulse Radiolysis Methods
Masatoshi Ukai and Y. Hatano
Chapter 7 Studies of Solvation Using Electrons and Anions in
Alcohol Solutions
Charles D. Jonah
Chapter 8 Electrons in Nonpolar Liquids
Richard A. Holroyd
Chapter 9 Interactions of Low-Energy Electrons with Atomic and
Molecular Solids
Andrew D. Bass and Leon Sanche
Chapter 10 ElectronIon Recombination in Condensed Matter:
Geminate and Bulk Recombination Processes
Mariusz Wojcik, M. Tachiya, S. Tagawa, and Y. Hatano
Chapter 11 Radical Ions in Liquids
Ilya A. Shkrob and Myran C. Sauer, Jr.
Chapter 12 The Radiation Chemistry of Liquid Water: Principles and
Applications
G. V. Buxton
Chapter 13 Photochemistry and Radiation Chemistry of Liquid Alkanes:
Formation and Decay of Low-Energy Excited States
L. Wojnarovits
Chapter 14 Radiation Chemical Eects of Heavy Ions
Jay A. LaVerne
Chapter 15 DNA Damage Dictates the Biological Consequences of
Ionizing Irradiation: The Chemical Pathways
William A. Bernhard and David M. Close
Chapter 16 Photon-Induced Biological Consequences
Katsumi Kobayashi
Chapter 17 Track Structure Studies of Biological Systems
Hooshang Nikjoo and Shuzo Uehara
Chapter 18 Microdosimetry and Its Medical Applications
Marco Zaider and John F. Dicello
Chapter 19 Charged Particle and Photon-Induced Reactions in Polymers
S. Tagawa, S. Seki, and T. Kozawa
Chapter 20 Charged Particle and Photon Interactions in Metal Clusters
and Photographic System Studies
Jacqueline Belloni and Mehran Mostafavi
Chapter 21 Application of Radiation Chemical Reactions to the Molecular
Design of Functional Organic Materials
Tsuneki Ichikawa
Chapter 22 Applications to Reaction Mechanism Studies of Organic
Systems
Tetsuro Majima
Chapter 23 Application of Radiation Chemistry to Nuclear Technology
Yosuke Katsumura
Chapter 24 Electron Beam Applications to Flue Gas Treatment
Hideki Namba
Chapter 25 Ion-Beam Therapy: Rationale, Achievements, and
Expectations
Andre Wambersie, John Gueulette, Dan T. L. Jones, and
Reinhard Gahbauer
Chapter 26 Food Irradiation
Jozsef Farkas
Chapter 27 New Applications of Ion Beams to Material, Space, and
Biological Science and Engineering
Mitsuhiro Fukuda, Hisayoshi Itoh, Takeshi Ohshima,
Masahiro Saidoh, and Atsushi Tanaka
Contributors
Andrew D. Bass University of Sherbrooke, Sherbrooke, Que bec, Canada
Jacqueline Belloni UMR CNRSUPS, Universite Paris-Sud, Orsay, France
William A. Bernhard University of Rochester, Rochester, New York, U.S.A.
G. V. Buxton University of Leeds, Leeds, England
David M. Close East Tennessee State University, Johnson City, Tennessee, U.S.A.
John F. Dicello Johns Hopkins University School of Medicine, Baltimore, Maryland,
U.S.A.
Jozsef Farkas Szent Istva n University, Budapest, Hungary
Mitsuhiro Fukuda Japan Atomic Energy Research Institute, Takasaki, Gunma, Japan
Reinhard Gahbauer Ohio State University, Columbus, Ohio, U.S.A.
John Gueulette Universite Catholique de Louvain, Brussels, Belgium
Y. Hatano Tokyo Institute of Technology, Tokyo, Japan
Richard A. Holroyd Brookhaven National Laboratory, Upton, New York, U.S.A.
Tsuneki Ichikawa Hokkaido University, Sapporo, Japan
Hisayoshi Itoh Japan Atomic Energy Research Institute, Takasaki, Gunma, Japan
Charles D. Jonah Argonne National Laboratory, Argonne, Illinois, U.S.A.
Dan T. L. Jones iThemba Laboratory for Accelerator Based Sciences, Somerset West,
South Africa
Yosuke Katsumura The University of Tokyo, Tokyo, Japan
Katsumi Kobayashi High Energy Accelerator Research Organization, Tsukuba, Japan
Noriyuki Kouchi Tokyo Institute of Technology, Tokyo, Japan
T. Kozawa Osaka University, Osaka, Japan
Jay A. LaVerne University of Notre Dame, Notre Dame, Indiana, U.S.A.
Tetsuro Majima Osaka University, Osaka, Japan
Mehran Mostafavi UMR CNRSUPS, Universite Paris-Sud, Orsay, France
A. Mozumder University of Notre Dame, Notre Dame, Indiana, U.S.A.
Hideki Namba Japan Atomic Energy Research Institute, Takasaki, Gunma, Japan
Hooshang Nikjoo Medical Research Council, Harwell, Oxfordshire, England
Takeshi Ohshima Japan Atomic Energy Research Institute, Takasaki, Gunma, Japan
Simon M. Pimblott University of Notre Dame, Notre Dame, Indiana, U.S.A.
Masahiro Saidoh Japan Atomic Energy Research Institute, Takasaki, Gunma, Japan
Leon Sanche* University of Sherbrooke, Sherbrooke, Que bec, Canada
Myran C. Sauer, Jr. Argonne National Laboratory, Argonne, Illinois, U.S.A.
S. Seki Osaka University, Osaka, Japan
IIya A. Shkrob Argonne National Laboratory, Argonne, Illinois, U.S.A.
M. Tachiya National Institute of Advanced Industrial Science and Technology (AIST),
Tsukuba, Japan
S. Tagawa Osaka University, Osaka, Japan
Atsushi Tanaka Japan Atomic Energy Research Institute, Takasaki, Gunma, Japan
Larry H. Toburen East Carolina University, Greenville, North Carolina, U.S.A.
Shuzo Uehara Kyushu University, Fukuoka, Japan
Masatoshi Ukai Tokyo University of Agriculture and Technology, Tokyo, Japan
Andre Wambersie Universite Catholique de Louvain, Brussels, Belgium
Mariusz Wojcik Technical University of Lodz, Lodz, Poland
L. Wojnarovits Hungarian Academy of Sciences, Budapest, Hungary
Marco Zaider Memorial Sloan-Kettering Cancer Center, New York, New York,
U.S.A.
*
Canada Chair in the Radiation Sciences.
1
Introduction
A. Mozumder
University of Notre Dame, Notre Dame, Indiana, U.S.A.
Y. Hatano
Tokyo, Japan
1. EARLY INVESTIGATIONS
The eect of visible and UV-light on matter, in vitro and in vivo, has a long history. In this
sense photochemistry and photobiology are forerunners, respectively, of radiation chem-
istry and radiation biology. The involvement of visible light on the discoloration of dyes
and on the growth and transformation of plants has been known since time immemorial.
In the 18th century the action of light on silver salts was denitely established, culminating
in rudimentary photography in the mid-19th century (see Chapter 20). Some qualitative
understanding of photochemical action was obtained by Grottus (1817) and by Draper
(1841) in which it was stated that only the absorbed light can be eective in bringing
out chemical transformation and that the rate of chemical change should be proportional
to the light intensity. With the advent of the quantum theory, Einstein (1912) formalized
what has since been called the rst law of photochemistry, i.e., only one quantum of light is
absorbed per reacting molecule. This actually applies to the primary process and at
relatively low light intensity to which all early studies were conned. Later work at high
intensity provided by lasers has necessitated some modication of this important law.
As not all primary activations are observable, the idea of the quantum yield or the number
of molecules transformed per quantum of light absorbed was introduced by Bodenstein
(1913) who also noticed chain reactions in the combination of hydrogen and chlorine
giving quantum yields many orders of magnitude greater than 1.
It is clear that, along with the discovery of x-rays in 1895, Roentgen also found the
chemical action of ionizing radiation. He drew attention to the similarity of the photo-
graphic eect induced by light and x-rays. Application to medicine appeared very quickly,
followed by industrial applications. However, this eld of investigation remained nameless
until Milton Burton, in 1942, christened it radiation chemistry to separate it from radio-
chemistry which is the study of radioactive nuclei. Historical and classical work in radia-
tion chemistry has been reviewed by Mozumder elsewhere [1]. Here we will only make a
few brief remarks.
Lind [2] has dened radiation chemistry as the science of the chemical eects brought
about by the absorption of ionizing radiation in matter. It should be distinguished from
radiation damage which refers to structural transformation induced by irradiation, par-
ticularly in the solid state. The distinction is not always maintained, perhaps uncon-
sciously, and sometimes both eects may be present simultaneously. Following a
suggestion of M. Curie around 1910, that ions were responsible for the chemical eects
of radioactive radiations, the symbol M/N was introduced to quantify the radiation
chemical eect, where M is the number of molecules transformed (created or destroyed)
and N is the number of ion pairs formed. Later, Burton [3] and others advocated the
notation G for the number of species produced or destroyed per 100 eV (=1.602 10
17
J)
absorption of ionizing radiation. It was purposely dened as a purely experimental
quantity independent of implied mechanism or assumed theory.
Bethe [4] rst pointed to the quantitative similarity of the excitation of a molecule by
light and by fast charged particle impact, thereby underscoring the importance of dipole
oscillator strength. Despite modications required for slower charged particles, this optical
approximation (see Sec. 3 and Chapters 2 and 5) remains a cornerstone in the understanding
of the primary processes in radiation chemistry. In the totality of the various eects brought
about by irradiation, the radiation chemical eects occupy a central position. In a similar
fashion electrons and photons are the most important agencies for bringing the radiation
eects. Electrons are always produced as secondary irradiation irrespective of the nature of
the primary ionizing particle. Photons are ubiquitous and, in any case, understanding of
charged particle impact requires a knowledge of photon impact processes.
Generally speaking, industrial applications of irradiation have a relatively short his-
tory except for some medical applications. The eld, however, has gained considerable
momentum since the 1960s. Spinks and Woods [5] have summarized radiation-induced
synthesis and processing; Mozumder [1] has also given a brief account of various appli-
cations to science and industry including dosimetry, food irradiation, waste treatment,
sterilization of medical equipment, etc. Salient features of radiation chemistry, both in the
gaseous and condensed phases, have been discussed in the CRC Handbook of Radiation
Chemistry edited by Tabata et al. [6]. Special topics of the interactions of excess electrons in
dielectric media have been adequately reviewed in a CRC handbook edited by Ferradini
and Jay-Gerin [7]. Further, specic applications to atomic and molecular processes in
reactive plasmas have been summarized by Hatano [8]. Chapters 15 through 27 of this book
are involved with radiation applications including radiobiological, medical, and industrial
applications. In addition, Chapters 16, 19, and 20 discuss, in considerable details, the eects
and applications of photon irradiation. An important role of synchrotron radiation (SR) as
a new photon source was theoretically pointed out for the rst time about 40 years ago by
R.L. Platzman and U. Fano. Recent progress in SR research has been remarkable, as
reviewed by Hatano elsewhere [9]. See also Chapter 5 for the newly established dedicated
SR facilities combined with new experimental methods for spectroscopy and dynamics.
2. TIME SCALE OF RADIATION ACTION
In the action of charged particle and photon irradiation on condensed matter, it is in-
structive to consider several stages of overlapping time scales. The stages, in ascending
orders of time, are called the physical, physicochemical, and chemical stages, respectively,
for radiation chemical studies. To these, biochemical and biological stages have been added
for application to radiobiology [10,11]. Within each stage various events take place
occupying their respective time scales. For example, within the biochemical stage (
f
10
3
to
f
10
+4
sec), secondary radicals form, evolve, and react, while the biological stage covers
a wide range of time frommitosis to late biological eect. The earliest discernible time, in the
physical stage, is obtained from the uncertainty principle, DEDt
f
,, as
f
10
17
sec, which
corresponds to the production of secondary electrons with energy z100 eV. Times such as
these or shorter are just computed values. The longest time scale in radiobiology may exceed
several years or generations if genetic eects are included. Morrison [12] rst gave an
approximate time scale of events for application to radiobiology. Several authors have
periodically updated the concept for dierent types of application. More recently, Lentle
and Singh [10] and Mozumder [11] have discussed this topic from the points of view of
radiation biology and radiation chemistry, respectively.
Table 1 summarizes some of the events that occur through the various stages. It
has been suggested that, following ionization in liquid water, the dry hole H
2
O
+
can
Table 1 Approximate Time Scale of Events in Radiation Chemistry, for Example, of Liquid
Water
log
10
t(sec) upt Event Stage
18 Fast electron traverses molecule
17 MeV proton traverses molecule;
energy loss to fast secondary
electrons.
fs 16 Energy loss to electronic states,
(Vertical excitation)
14 Fast ion-molecule reaction
(H-atom transfer). H
3
O
+
,
H and OH formed.
13 Solvated electron formed in water.
Longitudinal dielectric relaxation
in water. Molecular vibration.
Fast dissociation.
ps 12 Electron thermalized or trapped.
Spur formed. Self-diusion time
scales in simple liquids.
11 Transverse dielectric relaxation
time in water.
ns 9 Spur reactions continued.
8 Charge neutralization in media of
low viscosity. Secondary reactions
including intertrack reactions.
6 Electron escape time in low-viscosity
media. Intratrack reactions
completed. Secondary radical
formation and reaction.
0 Radiative lifetime of triplets.
Biochemical eects
3 Neutralization time for media at
very high viscosity. Time for mitosis.
Biochemical eects of metastables.
DNA synthesis time
Biological eects
Late biological eects
E
j
z
E
j
z
E
j
z
E
j
z
E
j
z
P
h
y
s
i
c
o
-
C
h
e
m
i
c
a
l
P
h
y
s
i
c
a
l
C
h
e
m
i
c
a
l
B
i
o
c
h
e
m
i
c
a
l
B
i
o
l
o
g
i
c
a
l
move by exact resonance until the ion-molecule reaction H
2
O
+
+H
2
O!H
3
O
+
+OH
localizes the hole. The earliest chemical transformation, indicated by H-atom transfer in
reactions of the type ROH
+
+ROH!ROH
2
+RO, then occurs in
f
10
14
sec in water
and alcohols [13]. The time needed for electron hydration is theoretically computed to be
f
0.2 psec [14] while experiment gives an upper limit of 0.3 psec [15]. The information
presented in Table 1 is not to be taken too literally. Each stage may contain many orders of
magnitude of time, but the usefulness of the time scale picture rests on the perception that
within an order of magnitude relatively few processes compete. As the species that exist at
the end of one stage serve as the input to the next stage, the qualication early is relative.
In radiobiological systems, the time of appearance of a change may be subjective depending
on the cell cycle, which is due to several dierent kinds of generations of biochemical and
biological transformations that must take place to render the radiation-induced transfor-
mation visible. Also, these processes can occur both in the directions of repair and ampli-
cation. Certain biochemical reactions, for example, that of OH with sugars, may occur in
the nanosecond time scale while others, such as those giving the O
2
eect, may take micro-
seconds. DNA strand breakage may be considered an early biological eect while other
damages can take
f
1 day to
f
40 years when genetic eects are considered. This should be
contrasted with
f
1 Asec needed for track dissolution in liquid water [16].
In the current millennium there is a strong need for interdisciplinary research involv-
ing an integrated outlook. In this sense various disciplines connected with radiation action
all start with radiation physics and radiation chemistry. From that point on one sees a
bifurcation. One way goes to radiation biochemistry to radiation biology and to medical
applications. Another way goes to engineering and industrial applications including, but
not limited to, polymerization, waste management, food preservation, etc.
3. FUNDAMENTAL PROCESSES IN THE PHYSICAL, PHYSICO-CHEMICAL,
AND CHEMICAL STAGES OF INTERACTIONS OF HIGH-ENERGY
CHARGED PARTICLES AND PHOTONS WITH MATTER
In the interactions of high-energy incident particles, i.e., photons, electrons, heavy charged
particles (or positive and negative ions), and other particles, with matter, the succession of
events that follow the absorption of their energies has been classied into three character-
istic temporal stages: physical, physico-chemical, and chemical stages [17] (see Sec. 2). The
physical stage consists of the primary activation of molecules in matter (in the case, for
example, it is composed of molecular compounds), due to the collision of high-energy
incident particles to form electronically excited or ionized states of molecules and ejected
electrons. The electrons thus formed may have sucient energy to further ionize the sur-
rounding molecules. At the end of the interactions, electrons are formed in a wide energy
range via cascading electronmolecule collision processes. These secondary electrons fur-
ther decrease their energies to the subexcitation energy range, leading to the formation of
reactive species, i.e., ions, excited molecules, free radicals, and low-energy electrons. These
species interact with each other or with stable molecules. Subexcitation electrons, which
are electrons below the rst excitation potential, degrade their energies by vibrational,
rotational, and/or elastic collisions to reach thermal energy. Electrons in the thermal and
epithermal ranges disappear predominantly by recombination, attachment, or diusion. It
is concluded therefore that a decisive step in the physical and physico-chemical stages of
the interactions of high-energy incident particles with matter is the collision of secondary
electrons with molecules in a wide energy range (see Chapters 25, 9, 17). The entire
feature of the fundamental processes of the interactions of high-energy incident particles
with molecules, i.e., the molecular processes in the physical and physico-chemical stages
(and further, the chemical stage which mainly consists of free radical reactions), are sum-
marized in Table 2 [18] (see Chapter 6).
Table 2 shows that molecules AB in collisions with electrons in a wide energy range
are directly ionized and excited into superexcited states [9] above their rst ionization
potentials (IP) and into excited states below IP. Superexcited states ABV are competitively
autoionized or dissociated into neutral fragments, i.e., free radicals or stable product
molecules (see Chapter 5). Electronically excited states AB* are also dissociated to neutral
fragments. Parent ions directly formed via ionization, or indirectly via autoionization, are
collisionally (and/or unimolecularly) stabilized or dissociated into fragment ions. Such
ions, particularly in the condensed phase, may be quickly neutralized with electrons by
geminate recombination or competitively converted to other ions via ionmolecule re-
actions (see Chapter 6), while in the gas phase such conversion is predominant compared
with recombination, depending on the pressure. In case of the addition of electronegative
solute molecules, negative ions are produced in electron attachment processes. Electrons
with characteristic energies are selectively captured by molecules to form negative ions (see
Chapter 6). It is generally accepted that molecular clusters, large aggregates of molecules,
and molecules in the condensed phase can capture electrons with large cross sections due
to electron attachment dynamics dierent from those in the gas phase for isolated single
molecules [19,20]. For polar molecules, electrons or ions are solvated with molecules to
form solvated electrons and ions, respectively (see Chapter 7). The recombination of
positive ions with electrons, particularly in the condensed phase, is classied as geminate
and bulk recombination processes (see Chapter 10). A relative importance of these two
processes is closely related with the transport mechanism of electrons in it, i.e., the mag-
Table 2 Fundamental Processes in the Physical, Physicochemical,
and Chemical Stages of the Interactions of High-Energy Charged
Particles and Photons with Molecules AB
AB

AB
+
+e
Direct ionization
ABV [Superexcitation (direct excitation)
AB
*
Excitation]
ABV
AB
+
+e
Autoionization
A+B Dissociation
AB
+
A
+
+B Ion dissociation
AB
+
+AB or S

Products Ionmolecule reaction
AB
+
+e
AB
*
Electronion recombination
AB
+
+S
Products Ionion recombination

e
+S

S
Electron attachment
e
+nAB
e
s
Solvation
AB
*
A+B Dissociation
AB Internal conversion and

intersystem crossing
BA Isomerization
AB+hr Fluorescence
AB
*
+S

AB+S
*
Energy transfer
AB
*
+AB
(AB)
2
Excimer formation
2A

A
2
Radical recombination
C+D Disproportionation
A+AB

A
2
B Addition
A
2
+B Abstraction
nitudes of the electron drift mobility or the electron conduction band energy in it. Phe-
nomenologically, it is more dependent on the properties of the medium molecules (see
Chapter 8). In some cases, particularly in admixed systems both in the gas and condensed
phases, energy or charge transfer processes may predominantly occur from molecules of
the major component in the system to added solute molecules (see Chapter 6).
As described above, a crucial step of the physical and physicochemical stages is the
collision of secondary electrons with molecules in a wide energy range. Therefore the infor-
mation on electronmolecule collision cross-section data, which must be correct, absolute,
and comprehensive, is of great importance and is helpful for understanding the essential
features of the fundamental processes in these two stages [21]. Such information is avail-
able both experimentally and theoretically in the gas-phase (see Chapter 3), but in some
cases also in the condensed-phase as well (see Chapter 9). Cross sections for the ionization
and excitation of molecules in collisions with electrons in the energy range greater than
about 10
2
eV are well elucidated quantitatively by the BornBethe theory [22]. This theory
is also helpful for calculating, at least roughly, these cross-section values further in the
lower energy range.
According to the optical approximation, which was shown by Platzman [23] to be
based on the BornBethe theory, a radiation chemical yield Gmay be estimated fromoptical
data, viz., photoabsorption cross sections, oscillator strength distributions, photoionization
cross sections, and photodissociation cross sections of molecules in a wide range of the
photon energy or wavelength, particularly in VUVSX region [9] (see Chapter 5). Basically,
this approximation should be applied only for a rough estimation of G values. Such a
limitation may be attributed to a supercial comparison of radiation chemical yields for
atomic systems with electronatom cross-section data in a limited collision-energy range
which were available in earlier stages of the related research elds in the 1960s. Recently,
however, its applicability has been examined by comparing electron-collision cross sections
for molecules in a wide collision energy range between optically allowed and forbidden
transitions, providing the conclusion, at least tentatively, that this approximation may be
applicable to the estimation of G values more precisely than previously considered [24].
There is a great need to examine the applicability more systematically because of recent
progress in the experimental and theoretical investigations of electronmolecule collision
processes [21].
The experimental and theoretical investigations of the physical, physico-chemical,
and chemical stages of the interactions of high-energy incident particles with matter have
made a remarkable contribution to recent progress in fundamental studies of the static and
dynamic behavior of reactive species, i.e., electrons, ions, excited atoms and molecules, and
free radicals. Conversely, these are needed for a comprehensive understanding of recent
progress in the fundamental studies of reactive species, where a scientically reasonable
analysis of the interesting but complex mechanism of the interactions of high-energy inci-
dent particles with matter is involved. Thus it often provides newndings of reactive species
as well as their static or dynamic behavior. For that purpose, the matrix representation is
helpful for summarizing or surveying the diverse information on such fundamental studies
of a variety of reactive species [18].
4. FIELDS OF STUDY: RELEVANCE TO BASIC AND APPLIED SCIENCES
The elds of study undertaken in the present book are rather broad. However, the con-
tributors, recognized experts in their respective areas, have striven to ensure continuity by
connecting important concepts to adjacent areas. Thus, in one example, the logical ow
would be from physics to chemistry to biology and medicine, and in another example it
could be from physics to chemistry to industrial applications, including polymerization,
waste, and ue-gas treatment, etc. In choosing the subject matters it has been the objective
of the editors that comparable importance is given to fundamentals and applications.
While it has been well recognized by almost everyone that radiation eect starts with a
physical interaction, very often followed by chemical reactions, etc., the chemical stage is
sometimes understressed in radiobiological discussions [25]. In a similar vein, the applied
radiation scientist may have a right to think that aqueous radiation chemistry has been
overstressed by the physical chemists who claim it to be a better understood topic in
chemical kinetics [26]. In any case the editors have taken care so that each signicant area
of investigation would receive comparable attention.
Studies in radiation science and technology may be viewed from three angles,
namely, life, industry, and basic knowledge. According to some estimates [27], the
continual exposure to environmental radiation over geological periods is important and
must be taken into account. There is now a widespread belief that aging and, indeed, the
genetic evolution of man may be signicantly inuenced by ambient radiation. Under-
standing of these eects duly belongs to radiation biology, which depends on radiation
physics and radiation chemistry for basic information. Radiation is applied in industry in
various waysfor example, as reaction initiators, sustainers, and also as control mech-
anisms. Some of the important ones are included in this book, while others, such as curing
of paints, materials for textile nishing, applications in mining and metallurgy, etc., are left
out for obvious space limitation. Finally, the important contribution made by radiation
chemistry to experimental basic science should be appreciated in making available
excitations to states which would otherwise be inaccessible by thermal activation.
REFERENCES
1. Mozumder, A. Fundamentals of Radiation Chemistry; Academic Press: San Diego, 1999.
2. Lind, S.C. Radiation Chemistry of Gases; Reinhold Publishing Corporation: New York, 1961.
3. Burton, M. J. Phys. Colloid. Chem. 1947, 51, 611.
4. Bethe, H.A. Ann. Physik. 1930, 5, 325.
5. Spinks, J.W.T.; Woods, R.J. An Introduction to Radiation Chemistry. 3rd ed. Wiley-Inter-
science: New York, 1991.
6. Handbook of Radiation Chemistry; Tabata, Y., Ito, Y., Tagawa, S., Eds.; CRC Press: Boca
Raton, 1991.
7. Excess Electrons in Dielectric Media; Ferradini, C., Jay-Gerin, J.-P., Eds.; CRC Press: Boca
Raton, 1991.
8. Hatano, Y. Adv. At. Mol. Opt. Phys. 2000, 43, 231.
9. Hatano, Y. Phys. Rep. 1999, 313, 109.
10. Lentle, B.; Singh, H. Radiat. Phys. Chem. 1984, 24, 267.
11. Mozumder, A. Radiat. Res. 1985, 104, S-33.
12. Morrison, P. Symposium in Radiobiology: The Basic Aspects of Radiation Eects on Living
Systems; In Nickson, J.J., Ed.; Wiley: New York, 1952; 112.
13. Magee, J.L.; Chatterjee, A. Radiation Chemistry: Principles and Applications; Farhataziz,
Rodgers, M.A.J., Eds.; Chap. 5. VCH Publishers: New York, NY, 1987.
14. Mozumder, A. J. Chem. Phys. 1969, 50, 3153.
15. Wiesenfeld, J.M.; Ippen, E.D. Chem. Phys. Lett. 1980, 73, 47.
16. Turner, J.E.; Magee, J.L.; Wright, H.A.; Chatterjee, A.; Hamm, R.N.; Ritchie, R.H. Radiat.
Res. 1983, 96, 437.
17. Platzman, R.L. Vortex 1962, 23, 327.
18. Hatano, Y. In: Handbook of Radiation Chemistry; Tabata, Y. Ito, Y., Tagawa, S., Eds.; CRC
Press: Boca Raton, 1991.
19. Hatano, Y. In: Electronic and Atomic Collisions; Lorents, D.C. Meyerhof, W.E., Peterson,
J.R., Eds.; Elsevier: Amsterdam, 1986; 153 pp.
20. Hatano, Y. Aust J Phys 1997, 50, 615.
21. Inokuti, M., Ed. In: Atomic and Molecular Data for Radiotherapy and Radiation Research;
IAEA-TECDOC-799 IAEA: Vienna, 1995.
22. Inokuti, M. Rev. Mod. Phys. 1971, 43, 297.
23. Platzman, R.L. Radiat. Res. 1962, 17, 419.
24. Hatano, Y. Radiat Phys Chem, to be published in 2003.
25. Lea, D.E. In: Actions of Radiations on Living Cells; Second ed. University Press: Cambridge,
1956.
26. Allen, A.O. In: The Radiation Chemistry of Water and Aqueous Solutions; D. Van Nostrand:
Princeton, 1961.
27. Vereshchinskii, I.V.; Pikaev, A.K. In: Introduction to Radiation Chemistry (translated from
Russian); Daniel Davey: New York, 1964.
2
Interaction of Fast Charged Particles
with Matter
A. Mozumder
1. ENERGY TRANSFER FROM FAST CHARGED PARTICLES
1.1. General Features
Any momentum change of an incident particle constitutes a collision. In the interaction of
an incident particle with an atom or a molecule, the collisions are classied as elastic or
inelastic. In elastic collisions, energy and momentum are conserved between the external
degrees of freedom (e.g., translation) of the colliding partners. In inelastic collisions, en-
ergy is transferred into, or from, the internal degrees of freedom of the struck molecule,
designated as collisions of the rst and the second kind, respectively. Because collisions of
the second kind are important for epithermal and thermal particles alone, we will only be
concerned with the collisions of the rst kind in this chapter. Furthermore, akin to the
Grottus principle (see the Introduction) in photochemistry, only the energy absorbed by a
molecule can bring about radiationchemical change, or the ensuing radiobiological trans-
formation. Therefore the internal molecular excitation (electronic, vibrational, etc.) is a
necessary precursor of radiation-induced transformation. In this context, ionization is in-
cluded as an extreme form of electronic excitation.
Particles and waves are distinguished only in classical mechanics. In quantum me-
chanics they are interchangeable, giving rise to rst and second quantizations, respectively.
However, it is customary to group the incident radiations as light (electrons, muons, x-
and g-rays, etc.) or heavy (protons, a-particles, ssion fragments, etc.) particles. Photons,
classied as a separate group, can cause excitation and ionization in a molecule. Ionization
by photons can proceed by any of the three following mechanisms: photoelectric eect,
Compton eect, and pair production. In the photoelectric eect, the photon is absorbed and
the emergent electron inherits the photon energy reduced by the sum of the binding energy
of the electron and any residual energy left in the resultant positive ion (Einstein equation).
In the Compton eect, the photon is scattered with signicantly lower energy by a medium
electron, which is then ejected with the energy dierence. In the pair production process,
the photon is annihilated in a nuclear interaction, giving rise to an electronpositron pair,
which together carries the photon energy lessened by twice the rest energy of the electron.
This process therefore has an energetic threshold. With increase in photon energy, the
dominant interaction changes from photoelectric to Compton to pair production. For
60
Co-g rays, almost the entire interaction is induced by the Compton eect which, by the
KleinNishina theory, gives a nearly at electron energy spectrum. Thus the 1.2-MeV
photon generates a wide spectrum of Compton electrons having an average energy of
f0.6 MeV; consequently, the medium molecules respond as if being showered by these
fast electrons. Pair production is a characteristic of very high energy photons; again, to the
medium molecules, the eect is the same as a spectrum of fast electrons and positrons of
appropriate energy. Electrons of various energy are the most important sources as primary
radiations in the laboratory and in the industry [1], and also as secondary radiations in any
form of ionizing event. Other often-used irradiations include x-rays, radioactive radiations
(a, h, or g), protons, deuterons, various accelerated stripped nuclei, and ssion fragments.
X-rays dier from g-rays operationally, i.e., x-rays are generated by machines whereas g-
rays are produced in nuclear transformations.
At ultrarelativistic speeds (vfc, the speed of light), a radiative process, called the
nuclear bremsstralung, becomes signicant. Bethe and Heitler [2] estimated the ratio of
energy losses of a charged particle due to radiative (bremsstralung) and collisional (elec-
tronic) processes at an energy of E MeV approximately as EZ/800, where Z is the nuclear
charge. For electrons in water, this radiative process only becomes signicant above 100
MeV. For the vast majority of cases with incident velocity f0.99c down to about the
speed of a least-bound electron, the dominant energy transfer mechanism is by electrosta-
tic and electromagnetic interactions between the incident charged particle and the medium
electrons. Of these, the electromagnetic interaction becomes important only at relativistic
speeds [3]. Therefore in most cases of importance to radiation science, the principal
interaction of an incident-charged particle with the medium electrons is of electrostatic
origin.
For fast charged particles impinging on matter, the very rst discernible eect is the
electronic excitation of molecules or atoms. Because electron is the lightest particle, its
excitation occurs at the earliest time scale consistent with the uncertainty principle, i.e., in
f10
16
sec. Later, transformation of the deposited energy in the various internal degrees
of freedom occurs in their respective time scale, e.g., in f10
12
sec for vibration, etc. Some
details were presented elsewhere [4]. Molecular dissociation and low-grade heat appear at
longer time scales and, in some cases involving exothermal reactions, the level of low grade
heat can terminate above that of absorbed electronic energy. There is no evidence of local
rise of temperature for fast incident charged particles.
1.2. Radiation Physics and Radiation Chemistry
Although in nature there is no distinction between physical and chemical eects, in
practice it is protable, depending on the investigators choice of discipline, to view the
radiation eect either from the point of view of the incident particle or from that of the
medium molecules, designated as radiation physics and radiation chemistry, respectively.
Thus the study of the charge, rate of energy loss, range, and penetration, etc. of the
incident particle, any of which may change under the interaction, constitutes radiation
physics. Study of the matter receiving the absorbed energy to produce chemical changes,
charge separation, luminescence, etc. essentially belong to radiation chemistry. It is evident
that radiation chemistry is the link between radiation physics and radiation biology (see
Ch. 1, Sec. 2). Some investigators recognize this link explicitly [5,6], while others short
circuit the chemical part, working directly from the physics of energy deposition to
biological eects [7]. That necessitates the introduction of additional parameters, such as a
critical dose or concepts such as microdosimetry [8,9].
1.3. Condensed Matter: Localization of Deposited Energy
Fano [10] drew attention to the fact that, derived from the uncertainty relation, an energy
loss f15 eV from a high-speed (fc) particle cannot be localized within f90 nm. That
such energy losses in a condensed medium would give rise to collective excitations
(plasmons) was a source of some concern until recently. On the other hand, understanding
of radiation-induced transformations, operation of detectors, etc. would require that the
deposited energy be localized in a molecule before dissociation or ionization can occur.
Because no reasonable explanation has yet been proposed for the localization of energy
after the initial delocalization, rationalization has been advanced as the delocalization
applying only to the rst interaction [4]. After that, all energy losses are localized and
correlated on a track [11].
Nevertheless, certain collective excitations can occur in the condensed phase. These
may be brought about by longitudinal coulombic interaction (plasmons in thin lms) or by
transverse interaction, as in the 7-eV excitation in condensed benzene, which is believed to
be an exciton [12]. Special conditions must be satised by the real and imaginary parts of
the dielectric function of the condensed phase for collective excitations to occur. After
analyzing these factors, it has been concluded that in most ordinary liquids such as water,
collective excitations would not result by interaction of fast charged particles [13,14].
2. STOPPING POWER, LET, AND FLUCTUATIONS
2.1. Bohrs Theory and the Bragg Rule
The rate of energy loss of a charged particle per unit pathlength is called the linear energy
transfer (LET). The corresponding energy received by the medium, which remains in the
vicinity of the particle track, is designated as the stopping power. Therefore LET and
stopping power refer to the penetrating particle and the medium, respectively. The dif-
ference between these quantities arises because, even in the shortest time scale (f10
15
s),
some of the deposited energy may be removed from the track vicinity by fast secondary
electrons, by Cerenkov radiation, and, in the case of ultrarelativstic particles, by bremss-
tralung. Cerenkov radiation is seen as a faint bluish light when the speed of the penetrating
particle (usually an electron) exceeds the group velocity of light in the medium. Although
it contributes negligibly to the LET, it has importance as a time marker, because it is
emitted almost instantaneously. The term LET was rst coined by Zirkle et al. [15] in a
radiobiological context, replacing some earlier nebulous terminology. Both LET and
stopping power are average concepts and considerable uctuations are to be expected
around these values. The physical theories of energy loss rate should refer to LET, but
these are often called stopping power theories. The International Commission on Ra-
diation Units and Measurements recommends the use of the symbol L
A
to denote energy
transfers below a limit A. Thus L
100
would denote LET for energy losses of less than 100
eV and L
l
would include all energy losses.
The rst successful theory of stopping power is attributed to Bohr [16,17]. He takes
the simplest case of a fast, yet nonrelativistic, heavy particle of velocity v and charge ze,
where e is the electronic charge. Under this condition, the basic electrostatic interaction
can be treated as a perturbation, that is, the particle path can be considered to be virtually
undeected. In addition, the energy losses occur through quasi-continuous inelastic col-
lisions with medium electrons, so that the average stopping power is a good representation
of the statistical process of energy loss. All stopping power theories recognize these sim-
plications. Neglecting the binding energy of the electron and calling the distance of
closest approach of the incident particle as the impact parameter b, it may be shown that
the component of momentum transfer parallel to the particle trajectory vanishes by
symmetry and that, perpendicular to the trajectory, is given by 2ze
2
/bv [18]. The same
expression is obtained by multiplying the peak force ze
2
/b
2
with the so-dened duration
of collision 2b/v. Thus the energy transfer is given by Q = (2ze
2
/bv)
2
/2m = 2z
2
e
4
/mb
2
v
2
,
where m is the electron mass. The dierential cross-section for this process is given geo-
metrically as:
dr pdb
2
2pz
2
e
4
=mv
2
dQ=Q
2
;
which is just the Rutherford cross-section for scattering by free charges receiving the
energy transfer Q. For application to bound electrons which can be excited (or ionized),
for the same momentum transfer, to the nth state with energy E
n
, Bohr surmised the sum
rule A
n
f
n
E
n
ZQ, where Z is the atomic number and f
n
is the oscillator strength of that
transition (see later for proper denition). The stopping power dE/dx is the energy loss
to all the medium electrons per unit path of the incident particle, over all permissible
energy transfers. Therefore
dE=dx N
_
dr
n
f
n
E
n
2pz
2
e
4
NZ=mv
2
lnQ
max
=Q
min
: 1
For the maximum energy transfer, binding eect may be ignored, giving in the non-
relativistic case Q
max
= 2mv
2
. For the minimum energy transfer, Bohr argued that col-
lisions must be sudden so that an eective energy loss may occur. That is, the collision time
2b/v must be Vt/E
1
, where E
1
is atypical atomic transition energy and t is Plancks
constant divided by 2p. This gives b
max
= tv/2E
1
and Q
min
= 8z
2
e
4
E
1
/[(mv
2
)(t
2
v
2
)]. Sub-
stituting in Eq. (1), one obtains
dE=dx 4pz
2
e
4
N=mv
2
B; 2
where the expression within the parentheses in Eq. (2) is called the kinematic factor and B,
denoted as the stopping number, is given in Bohrs theory as Z ln[(2mv
2
/E
1
)(tv/4ze
2
)].
Although the impact parameter is not an observable quantity, Bohrs theory has a wide
range of validity if the typical transition energy E
1
is properly chosen. Equation (2) also
shows the typical structure of a stopping power equation as a product of a kinematic
factor and a stopping number. The kinematic factor is free from any target property,
which is solely contained in the stopping number. In most stopping power expressions, the
kinematic factor therefore remains the same as in Eq. (2).
As it stands, Bohrs theory is only applicable to atoms. To extend it to molecules and
mixtures, one invokes the Bragg rule, originally used for charged particle ranges in ion-
ization chambers. Simply stated, the Bragg rule equates the stopping number of the mol-
ecule (or the mixture) to the weighted sum of the stopping numbers of the constituting
atoms. Braggs additivity rule applies impressively within a few percent for many com-
pounds. However, the contribution of an atomic stopping number in dierent compounds
is not necessarily the same as that for the free atom. That this contribution remains the
same in each case indicates the similarity of that atomic participation in various com-
pounds. The apparent success of Braggs rule has been traced to two factors: (1) similarity
of atomic binding in dierent molecules, and (2) electronic transitions that have the most
oscillator strengths involve excitation energies far in excess of chemical binding. Where
such is not the case as, for example, in H
2
, NO and compounds of the lightest elements, the
rule does not hold well. There is evidence that the Bragg rule starts to break down at low
incident energies. The quantum mechanical theories of stopping power are also amenable
to this additivity rule in a similar fashion (see Sec. 2.2). However, this does not mean that
the ensuing chemical response of the molecule is necessarily related to those of the con-
stituent atoms. There are denite eects of chemical binding and state of aggregation
which alter the energy levels and the oscillator strengths of transitions. The Bragg rule
refers only to the stopping of the incident particle.
2.2. Bethes Theory and Extensions
The rst (and still the foremost) quantum theory of stopping, attributed to Bethe [19,20],
considers the observables energy and momentum transfers as fundamental in the inter-
action of fast charged particles with atomic electrons. Taking the simplest case of a heavy,
fast, yet nonrelativistic incident projectile, the excitation cross-section is developed in the
rst Born approximation; that is, the incident particle is represented as a plane wave and
the scattered particle as a slightly perturbed wave. Representing the Coulombic interaction
as a Fourier integral over momentum transfer, Bethe derives the dierential Born cross-
section for excitation to the nth quantum state of the atom as follows.
dr
n
2pz
2
e
4
=mv
2
jF
n
qj
2
dQ=Q
2
3
In Eq. (3), q is the magnitude of the momentum transfer, Q = q
2
/2m is the energy of
a free electron having that momentum q, and other kinematic parameters have the same
signicance as in the Bohr theory. The quantity, F
n
q S
j
n exp2pihq r
j
0
_
, called the
inelastic form factor, is the sum over all the target electron coordinates, of the matrix
elements of the exponential operator involving the vector momentum transfer q between
the ground and the nth excited state. Obviously, the stopping power would be obtained
from Eq. (3) as dE=dx NS
n
m
Q
max
Q
min
E
n
dr
n
, where N is the atomic number density, E
n
is
the transition energy, and Q
min
and Q
max
stand for the minimum and maximum values of
Q, respectively, consistent with a given excitation energy. It is convenient to divide the
range of Q into small and large momentum transfers [3]. In collisions involving small
momentum transfers, sometimes called soft or glancing collisions, Bethe shows that
jF
n
( q)j
2
!Qf
n
/E
n
, where f
n
is the corresponding dipole (optical) oscillator strength (vide
infra). This allows the contribution of such collisions to the stopping power to be written
(cf. Eq. (3)) as 2pz
2
e
4
N=mv
2
S
n
f
n
ln
Q
1
E
2
n
=2mv
2
, where Q
1
is the rather inconsequential
upper limit of Q for small momentum transfers, and Q
min
, for excitation energy E
n
, is
given kinematically as E
2
n
/ 2mv
2
. For large momentum transfer collisions, sometimes de-
signated as hard or knock-on collisions, Bethe directly proves the sum rule S
n
E
n
j Fq
n
j
2
ZQ. Inserted into Eq. (3), one then obtains the contribution of hard collisions to the
stopping power as (2pz
2
e
4
N/mv
2
)Z ln(2mv
2
/Q
1
), where Q
1
is taken as the lower limit of Q
for hard collisions and the kinematic maximum 2mv
2
is used for Q
max
. Noting the
ThomasKuhn sum rule
S
n f
n
Z, the total number of electrons in the atom, and adding
the contributions of soft and hard collisions, the total stopping power is then given by
dE=dx 4pz
2
e
4
NZ=mv
2
ln2mv
2
=I; 4
where we used Bethes denition of the mean excitation potential I of the atom through
Eq. (5).
Z ln I
n
f
n
ln E
n
5
The basic stopping power formula of Bethe has a structure similar to that of Bohrs
classical theory [cf. Eq. (2)]. The kinematic factor remains the same while the stopping
number is given by B =Zln(2mv
2
/I) for incident heavy, nonrelativistic particles. The Bethe
theory gives a meaning to the mean excitation potential I in terms of strengths and ener-
gies of atomic transitions and underscores the importance of the dipole oscillator strength.
It should be noted that, in the denition of the mean excitation potential [Eq. (5)], as well
as in the derivation of the ThomasKuhn sum rule, excitation to energetically inaccessible
states are also formally included. At a suciently high incident velocity for the Born ap-
proximation to be valid, it usually does not entail much error. However, it is a separate
approximation. Another approximation, called Bethes asymptotic cross-section, derives
from expanding the interaction cross-section at high incident energies and retaining only
the lead term [21]. A simplied derivation of Bethes formula has been given by Magee
[22].
Several extensions of the basic stopping power theory of Bethe can be made. For
compounds and mixtures, Braggs additivity rule may be applied with the resultant value
of I given by the geometrical average of the mean excitation potentials of the constituent
atoms over their electron numbers. In the case of incident electrons, Q
max
, ignoring atomic
binding, would be given by (1/4)mv
2
rather than by 2mv
2
, because the distinction between
the incident and the secondary electron can only be made on the basis of energy.
Incorporating this modication, Bethe gives Belectron Z lnmv
2
=2
e=2I
_
, where e
is the base of natural logarithm. Thus the electron stopping power at the same velocity is
always a little less than that of a heavy particle, sometimes by as much as 20%.
At relativistic speeds, the maximum energy transfer increases to 2mv
2
/(1b
2
), where
b = v/c. Also, electromagnetic eects have to be considered in addition to electrostatic
interaction. These result in the addition of a term Z[ b
2
+ln(1b
2
)] to the stopping
number. This extra stopping, called the relativistic rise, is proportional to b
4
for small
values of b. Its eect is <0.1% for v<510
9
cm sec
1
, but it can be very signicant when
vfc. Fermi showed that the electronic stopping power would diverge were it not for the
mutual polarization screening of medium electrons. This eect, therefore, is more
important in the condensed phase and is called a density correction. This corrective
factor, added to the stopping number, is denoted by Zd/2, where d =ln[ tx
2
p
/I
2
(1b
2
)]1
and x
p
= (4kNe
2
Z/m)
1/2
, denoted as the plasma frequency [3]. Another correction is usu-
ally needed when the incident particle is not faster than the speed of atomic electrons, as
required for the validity of the Born approximation. This is more important for the K
electrons, but it is also sometimes needed for the L electrons in heavy elements. Denoting
the total so-dened shell correction as C, the result is a little reduction of the stopping
number by that amount. Combining the eects of relativity, density, and shell corrections,
the Bethe stopping number of a heavy particle is given by
B Zln 2mv
2
=I b
2
ln1 b
2
C=Z d=2: 6
The corresponding stopping number for the electron is given by
Belectron Z=2
_
ln mc
2
b
2
E=2I
2
I b
2

_
2
1 b
2
_
1 b
2
_
ln 2
1 b
2
1=8
_
1
1 b
2
_
_
2
2C=Z d
_
7
where E is the electron energy at velocity bc. Because electrons can acquire relativistic
speed at moderate energies, say >20 keV, the required correction is more important for
electrons.
Slow positive ions tend to capture electrons from the medium when their speeds fall
below z
1
v
0
, where z
1
is the bare nuclear charge and v
0
is Bohrs velocity. At rst, the
captured electron is promptly lost in a subsequent charge-changing collision. The cycle of
capture and loss continues for a while and an equilibrium charge is established. The
incident charge in the stopping number should then be changed from z to z
e
, given by
hz
2
i
1/2
, where the angular brackets indicate averaging with respect to charge-changing
collision cross-sections. After the rst electron is rmly captured, another cycle of electron
capture and loss may continue until a second electron is rmly captured, and so on. The
net eect of charge changing collisions is to lessen the stopping power a little because z
e
is
always <z. Even so, electron capture and loss constitute minor energy loss processes by
themselves.
Despite the apparent similarity of the Bohr and the Bethe stopping power formulae,
the conditions of their validity are rather complimentary than the same. Bloch [23] pointed
out that Born approximation requires the incident particle velocity v>>ze
2
/h, the speed of
a 1s electron around the incident electron while the requirement of Bohrs classical theory
is exactly the opposite. For heavy, slow particles, for example, ssion fragments penetrat-
ing light media, Bohrs formula has an inherent advantage, although the typical transition
energy has to be taken as an adjustable parameter.
2.3. Dipole and Generalized Oscillator Strengths: Sum Rules
From the inelastic form factor (see Sec. 2.2), Bethe [19] denes a generalized oscillator
strength f
n
( q) u E
n
F
n
( q)
2
/Q, for excitation with an energy loss E
n
, simultaneously with a
momentum transfer q, in close association with the (optical) dipole oscillator strength. The
latter may be obtained experimentally from the absorption coecient a(v), viz. f
n
= (mc/
pnVc
2
)ma(v)dv, where nV is the medium refractive index and the integration is carried over
the frequency v for the same transition. Theoretically, it is related to the dipole moment
matrix element for the transition from the ground to the nth state through the Einstein
Acoecient as f
n
8pmv=e
2
hg
n
hnje S
j
x
j
j0i
2
. Here g
n
is the degeneracy of the excited
state (the ground state is taken as nondegenerate), x
j
is the x component of the position of
the jth electron, and the summation is carried over all the atomic electrons. Expanding the
exponential in the inelastic form factor [see Eq. (3) et seq.] for a small momentum transfer,
and noting the orthogonality of the wave functions, one obtains lim
q!0
f
n
q f
n
, thus
establishing a relationship between the generalized and dipole oscillator strengths. Fig. 1
shows such a procedure for the electron impact excitation in helium at an incident energy
of 500 eV [24]. Platzman [25] advocated the construction of a complete optical spectrum
( f
n
), and therefrom, that of the excitation spectrum ( f
n
/E
n
) [cf. Eq. (3) and the denition of
the generalized oscillator strength], from a few experimental determinations augmented by
the various sum rules. However, the results in the cases of methane and water were not
very satisfactory, probably because of the unavailability of a sucient number of dipole
sums of adequate accuracy.
Both generalized and dipole oscillator strengths satisfy sum rules, which can be used
to unravel their character, although their calculation from rst principles is not easy except
for the lightest elements. For the dipole oscillator strength, a sum may be dened by
Sl
n
E
l
n
f
n
; 8
where the sum is over all the states of excitation, including integration over continuum
states (here and in later discussion). S(0) = Z, the number of electrons in the atom or
molecule. This is called the ThomasKuhn sum rule. Bethe [19] has shown that the same
rule is satised by the generalized oscillator strength for any momentum transfer,
i.e., S
n
E
l
n
F
n
q Z, for any q. Considering the oscillator strength as a normalized distri-
bution, S(l) in Eq. (8) may be taken as the lth moment of the transition energy. While
S(l) diverges for l z 3 in systems where the ground state electron density is nonvanishing
at the nucleus [21], for 4 Vl V2, the sums are related to important physical properties
[26]. S(4) may be experimentally obtained from the refractive index and the Verdet
constant, the latter referring to the rotation of the plane of polarization per unit thickness
per unit magnetic eld parallel to the propagation direction. S(2) = a/4, where a is the
polarizability. S(2) = (16pZ/3)times the average electron concentration at system center.
S(1) is related, apart from a constant ground state energy, to momentum correlation of
electrons [26]. S(1) equals the total dipole matrix element squared, M
2
tot
S
i; j
x
i
x
j
_
,
which appears as a lead term in the total inelastic collision cross-section [27].
Another class of sum rules may be dened as logarithmic moments, or by formally
dierentiating S(l) with respect to l [see Eq. (8)], yielding
Ll
n
E
l
n
f
n
ln E
n
Sl
d
dl
Sl: 9
L(0)=Z ln I, where I is the mean excitation potential appearing in Bethes stopping power
equation [Eq. (4)]. L(2) is proportional to the logarithm of average excitation energy,
which is also involved in the Lamb shift [26]. L(1) has been shown to be an optical
Figure 1 Generalized oscillator strength for the 1
1
S!2
1
Ptransition in heliumobtained by Lassettre
et al. [24], with 500-eV incident electrons. The abscissa is the square of the momentum transfer
in atomic unit (1.9910
19
g cm/s). Note that, according to the Lassettre procedure, lim
q!0
f
n
q f
n
,
the optical oscillator strength, is attained irrespective of the validity of the Born approximation.
However, if that approximatiom remains valid, then the curve of f
n
( q) would be independent of
incident energy.
quantity [27]. Oscillator strength sum rules have been used with success, limited chiey to
the lightest atoms, in amending uncertain oscillator strengths and in calculating a range of
physical properties including the refractive index and the Verdet constant [26]. Thus, for
example, the dipole oscillator strength of the transition 2
1
Pp1
1
S in helium was corrected
by Miller and Platzman [28] to 0.277, against an earlier calculated value of 0.19.
2.4. Special Features of the Condensed Phase
One aspect of the condensed phase regarding the delocalization of the deposited energy
has been alluded to in Sec. 1.3. Here we will consider the modications on the oscillator
strength and the mean excitation potential, due to condensation, which would enter in
Bethes stopping power theory [see Eqs. (47)].
For polyatomic molecules such as water, the oscillator strength is, in general,
continuously distributed because of any combination of dissociation, ionization, etc.
The stopping power is then determined by the dierential oscillator strength distribution
(DOSD). Phase eects occur naturally through the DOSD. In the gas phase, light
absorption and/or inelastic scattering experiments can be used to obtain the DOSD,
and a fairly complete determination has been made for water vapor [29]. In the condensed
phase (solid or liquid), absorption measurement in the far-UV and beyond is experimen-
tally very dicult. In such cases, an indirect method, depending on electromagnetic
relationships, can be sometimes used if reectance measurements are available at the
vacuumliquid (or vacuumsolid) interface over a wide range of energies. Denoting the
reectance at energy E as R(E), the phase angle is obtained from the KramersKronig
relation, /E E=pPm
l
0
ln REVdEVEV
2
E
2
1
, where P is Cauchys principal value
for the integral. From these, the real and imaginary parts of the refractive index are
obtained as n = (1R)/(1+R2R
1/2
cos /) and k = (2R
1/2
sin /)/(1R2R
1/2
cos /),
respectively. The real and imaginary parts of the dielectric function are then given by
e
1
= n
2
k
2
and e
2
= 2nk, with Im(1/e) = e
2
/(e
2
1
+e
2
2
). The DOSD f V(E) is nally calcu-
lated from the equation Im(1/e) = (h
2
e
2
NZ/2m) f V(E)/E. Here f V(E)dE is the oscillator
strength contained for transitions with energy between E and E+dE. In a certain sense
within the context of the Bethe theory, the function Im(1/e) is more fundamental for the
interaction in the condensed phase.
There is an upper limit of experimental reectance measurement, usually around 26
eV. With present-day synchrotron sources, this limit is being progressively extended.
Nevertheless, in the global integration of the KramersKronig relation, a long extrap-
olation is needed. In the original experiments of Heller et al. [30] on liquid water, an
exponential and a power-law extrapolation beyond the upper limit of experiments were
used. Later, LaVerne and Mozumder [31], requiring transparency in the visible region and
the correct number of valence electrons (8.2 for water), opted for the power-law with index
3.8, close to the theoretical limit of 4.0 for valence electrons. The contribution of the K
electrons remains the same as in the gas phase and are, therefore, simply added. The so-
determined DOSD for liquid water is shown in Fig. 2, and compared with that of the gas
phase given by Zeiss et al. [29], and with that of gaseous cyclohexane, obtained by
Koizumi et al. [32] by using synchrotron UV-absorption measurement. In water, there are
two main eects of condensation. First, there is a loss of structure in the condensed phase.
Second, there is an upward shift of the excitation energy. The peak in the DOSD changes
from f18 eV in the gas phase to f21 eV in the liquid phase. This means that collisions in
the liquid phase are more dicult. Using the oscillator distribution, the computed values
of I, the mean excitation potential is 74.9 and 71.4 eV for liquid and gaseous water,
respectively [31]. This dierence may not seem critical in determining the stopping power.
However, the nature and energy of the excited states are dierent in the two phases,
yielding dierent chemical outcomes (see later).
2.5. RangeEnergy Relation
The range of an incident particle is dened as the average crooked path length between the
initial and nal energies, while penetration refers to the vector distance between the
starting and ending points. The dierence between these quantities is attributed to
scattering, mostly elastic. Obviously, range increases with initial energy. The rangeenergy
relation is important for the identication and energy measurement of charged particles, a
tool that is routinely used in nuclear physics. In radiation chemistry, it provides a basis for
charged particle tracks and the reactions on them. Various tables of ranges of light and
heavy particles are now available, of which an earlier collection [33] and a later
compilation by Ziegler [34] are noteworthy.
Range, obtained by (numerical) integration of the stopping power as, R m
E
i
E
0
dE=
dE=dx, is called the continuous slowing down approximation (CSDA) range. Here E
i
is the initial energy, E
0
is the energy where the particle is considered stopped, and the
approximation refers to the stopping power being a continuous function of energy,
ignoring random uctuations. For electronic stopping, E
0
should be the energy of the
rst excited state, but a higher value is often adopted for fast incident particles, because, at
Figure 2 Dipole oscillator strength distribution in gaseous water [29, curve, A], in liquid water [31,
curve, B] and in gaseous cyclohexane [32, curve, C]. Data in liquid water are obtained from an
analysis of UV-reectance and that in cyclohexane, from synchrotronUV absorption. The Thomas
Kuhn sum rule is satised approximately in each case.
low energies, the stopping power formula is not reliable and, in any case, it is superseded
by subelectronic processes. Such an arbitrary value of E
0
becomes inconsequential if the
incident energy is suciently high.
Often, the rangeenergy relation is displayed as a power law, R~E
m
, where the index
m would approach 2 if the slow variation of the stopping number B with particle velocity is
ignored [see Eq. (4) et seq.]. For protons and He ions of a few hundred MeV, m
approaches 1.8, decreasing somewhat with decreasing energy. The index m also depends
on the medium traversed. For electrons in water, it diminishes gradually from f1.7 to
f0.9 as the initial energy is decreased from a few thousand to a few hundred eV. Low-
energy electron range in water is of great importance to the spur theory of radiation
chemistry, but it is also rather dicult to ascertain and often greatly inuenced by elastic
scattering. This eld is being continually improved and track simulation techniques have
been employed [35], which give not only the mean range, but also its distribution (see the
next section). However, very little is known about elastic scattering in liquid water, forcing
many investigators to use gas phase data for that purpose. Typical values of computed
ranges in water are f550 nm for 5-keV electrons, f0.5 mm for 5-MeV protons, and
f0.04 mm for 5-MeV a-particles. Ranges of slow heavy ions and ssion fragments are
nearly proportional to energy, because the increase of stopping power in relation to
slowing down is largely compensated by a lowering of eective charge as a result of
electron capture, thus providing an almost constant stopping power. The typical density-
normalized range of Ne ions of 10 MeV/amu in Al is 40 mg/cm
2
.
2.6. Discussion of Stopping Power, Range, and Fluctuations
The most important factor in Bethes stopping power equation, which embodies the
aggregate eect of transition energies and oscillator strengths, is the mean excitation
potential, I [see Eqs. (4) and (5)]. Its direct calculation requires the knowledge of the
ground and all excited state wave functions. Such a calculation for atomic hydrogen gives
I = 15 eV, whereas in atomic binding in dierent molecules, a value of 18 eV is preferred
to satisfy the Bragg rule [3]. For other atoms, application of the ThomasFermi model by
Bloch shows that the spectral distribution of the oscillator strength has universal shape in
all atoms, if the transition energy is scaled by Z. This means I~Z, with the constant of
proportionality being f12 eV. A detailed examination of the ThomasFermiDirac model
gives I/Z = a+bZ
2/3
, with a = 9.2 and b = 4.5 as best adjusted values, and where I is
expressed in eV. This equation agrees rather well with range experiments. However, Fano
[3] points out that it should not be construed as a validation of the statistical model of the
atom. I, being a logarithmically averaged quantity, can be well approximated without an
accurate knowledge of the distribution. An error yI in determining I only appears as a
relative error of f(1/5)yI/I in the evaluation of range. In practice, I is often treated as an
adjustable parameter to be xed by range measurement of fast protons or a-particles. With
known I values of constituent atoms, the mean excitation potential of a molecule may be
obtained by the application of the Bragg rule (see Sec. 2.1). Thus if the molecule has n
I
atoms of atomic number Z
I
, and mean excitation potential I
I
, then the overall mean
excitation potential of the molecule would be given by the relation Z ln I = Sn
i
Z
i
ln I
i
,
where Z = Sn
i
Z
i
is the total number of electrons in the molecule.
The stopping power of water, over a wide span of energy, for various incident
particles has been discussed elsewhere [Ref. [4], Sec. 6], with special consideration for
eects at low and very high energies. Generally speaking, the electronic stopping power
shows a peak at a relatively low energy (f100 eV for incident electrons and f1 MeV for
incident protons), as a result of the combined eect of the velocity denominator in the
kinematic factor and the logarithmic velocity dependence in the stopping number [c.f., Eq.
(4) et seq.].
The usual stopping power formula for low-energy electrons (BornBethe approx-
imation) requires corrections on two accounts. First, the integrals dening the total
oscillator strength and the mean excitation potential must be truncated at the maximum
energy transfer (c(1/4)mv
2
), resulting in the replacement of Z and I by Z
e
and I
e
,
respectively[36]. These quantities are lower than their respective asymptotic values and
their eects partially cancel each other. Second, the eect of the nonvanishing of the
momentum transfer for inelastic collisions becomes signicant. When a quadratic exten-
sion of the generalized oscillator strength is made in the energy-momentum plane still
using the DOSD, the net eect is expressible as a reduction of the electron stopping
number by an amount Z
e
(e/2E)ln(4e E/I ), where e is the base of natural logarithm, E is
incident electron energy, e is average energy loss in an encounter, and I is a mean energy
dened by Z
eff
e ln I m
0
e
max
e ln efede [36]. Here e
max
is the maximum transferable ener-
gy. In track simulation procedure, it is more convenient to work with basic cross-sections
(with which the stopping power is calculated) and keep a detailed account of energy loss,
distance traversed, etc. The stopping power may then be computed from denition by
averaging over a large number (typically f10
4
) of simulations. The results of such a
calculation by Pimblott et al. [35] is shown in Fig. 3 for water in the gaseous and liquid
phases. The dierence, of course, is directly traceable to that in the DOSD as discussed
earlier.
Even if the statistical uctuation of energy loss is ignored, there would be a dierence
between the CSDA range and the penetration, because of large-angle elastic scattering (see
Sec. 2.5). The distribution of the nal position vector of the penetrating particle can be
obtained in terms of its energy-dependent stopping power and the dierential cross-section
of scattering [36]. Actual calculation in the general case is complex, but it simplies con-
siderably when the number of scatterings are >>1. The distribution can then be shown as
gaussian and spheroidal, i.e., W(r) =(2pA)
1
(2pB)
1/2
exp[{(x
2
+y
2
)/2A+(zhzi)
2
/2B}],
where A=hx
2
i and B=hz
2
ihzi
2
, and the angular brackets refer to mean values. The
mean square radial penetration is then given by r
2
_
2pm
l
0
r
4
drm
p
0
Wrsin hdh, where h is
the angle of the position vector relative to the z-axis, the initial direction of motion. The
root mean square (rms) range, dened by hr
2
i
1/2
is often the more signicant quantity.
Fig. 4 shows the CDSA and rms ranges in gaseous water as functions of electron energy
according to LaVerne and Mozumder [36]. In these calculations, stopping power was com-
puted by the procedure detailed above. The scattering cross-section was tted to swarm
and beam data by adopting Molieres modication of screened Rutherford scattering. It is
obvious that the rms range is always shorter than the CSDArange, the dierence becoming
more signicant at lower energies. The following general observations can be made for the
penetration distribution. (1) The memory of the initial direction is maintained by the
electron until it has lost f80% of the starting energy, after which the distribution becomes
spherical. (2) The electron penetrates a certain distance with only a few scatterings and then
diusive motion sets in. (3) The number of elastic scatterings needed to give a spherical
distribution increases with energy, being f15 and f74, respectively, for electrons of 1 and
10 keV energy in water.
Because of the statistical nature of collision processes, charged particles starting with
the same energy do not travel the same distance after losing a xed amount of energy, nor
do they have the same energy after traveling a xed distance, respectively giving rise to
pathlength straggling and energy straggling. Fano [3] adds a third kind of distribution of
distance for particles that have dropped below a certain energy at the last collision, which
is not necessarily the same as pathlength straggling, because of the discrete nature of the
energy loss process. While all these distributions are related, the most important
distribution is range straggling when the nal energy is reduced to insignicance. Bohr
[17] considers a group of energy losses and a large number of loss processes in each group,
thereby obtaining a gaussian distribution by virtue of the central limit theorem. This
means (d/dx)hDE
2
i =4pe
4
z
2
NZ, where hDE
2
i is the mean square uctuation in energy loss
of particles after traversing a distance x. The corresponding pathlength and range
distributions are also gaussian. These considerations apply mainly to heavy particles of
relatively high energy penetrating virgin media. The ratio of the root mean square range
dispersion to the mean range is typically a few percent for a heavy particle, but may be a
few tens of percent for electrons of moderate energy. Straggling is always more important
for electrons of any energy because of the large fractional energy that an electron can lose
in a single encounter. Also, if the sample penetrated is thin, the resultant energy
Figure 3 Density-normalized stopping power (MeV
cm
2
/g) of gaseous and liquid water as a
function of electron energy according to track simulation by Pimblott et al. [35]. There is a noticeable
phase eect, while a peak is seen at f100 eV in both phases.
distribution of emergent particles of any kind will not be gaussian, but will show a high
energy tail. Such LandauVavilov distribution has been extensively tabulated [33], having
experimental justication. Its application to radiation biology derives from the fact that
the radiation eect in a cell depends on the energy deposited in it, while the cell size is often
small compared to the particle range [37].
A collision-by-collision approach was introduced by Mozumder and LaVerne [38]
for range straggling of low-energy electrons without the consideration of large-angle
elastic scattering. The probability density of pathlength x for the rst collision is given by
P
1
(x) = K
1
exp(x/K), where the mean free path K is computed from the same dier-
ential cross-section of energy loss as used in the stopping power (vide supra). The integral
of the energy-loss weighted dierential cross-section hei gives the mean energy loss in a
single inelastic encounter. The ratio, hei/K, gives the spatial rate of energy loss for that
encounter, while the true stopping power is the mean value of the ratio of energy loss to
path length. To this extent, the procedure is an approximation. To have a pathlength
distribution P
n
(x) in n collisions, the electron must have had a distribution P
n1
(xy) in
(n1) collisions and a distribution P
1
( y) in the last collision. This generates a convolution,
P
n
x m
x
0
P
n1
x yP
1
ydy. By repeatedly using the Laplace transform method, one
can evaluate the integral with the result: P
n
x S
n
i1
K
1
i
S
n
i
expx=K
i
, where S
n
i

C
n
j1
1 K
j
=K
i
1
j p 1. Note that the mean free paths are energy-dependent. Therefore
a concurrent use of the stopping power is required to give the electron energy after each
collision. To obtain the range distribution, the total number of collisions is so adjusted
that the mean nal energy becomes immaterial. Thus, as shown in Fig. 5, Mozumder and
LaVerne [38] give the range distribution of 200-eV electrons in N
2
by convoluting the
pathlength distributions between energies 200 to 110 eV and between energies 110 to 31
eV. In this case, the nal energy has been taken to be twice the ionization potential. Notice
Figure 4 Continuous slowing down (CSDA) range and root mean square (rms) penetration in
gaseous water according to LaVerne and Mozumder [36]. See text for details.
that, in these calculations, the fundamental input still remains to be the DOSD. The
following remarks may be made about the range distribution of low-energy electrons. (1)
For electron energies below about 5 keV, CSDA>mean>median range. CSDA range is
the least reliable because it considers energy losses in a continuous manner within the
mean free path. (2) At low energies, the distribution is skewed toward longer ranges. The
skewness parameter approaches the gaussian limit of unity above f10 keV, almost
independent of the material traversed. (3) The most probable density-normalized range
for a 1-keV electron in H
2
O, N
2
and O
2
is 6.1, 7.1, and 8.4 Ag/cm
2
, respectively. However,
relative straggling, given by the ratio of FWHM of the range distribution to the most
probable value, is nearly independent of the medium, being 1.4, 0.7, and 0.4 at energies of
100, 500, and 2000 eV, respectively.
So far, the discussion presented here is based either on penetration deriving from
large angle elastic scattering, or on the statistical nature of inelastic collisions giving
straggling. As yet, there has not been any analytic theory that combines both, but Monte
Carlo simulation, including some form of realistic dierential cross-section of elastic
scattering, shows promise [35].
3. SECONDARY IONIZATION
3.1. Cross-Sections
Ionizations produced by electrons generated in the primary interaction of the incident fast
charged particle are called secondary. The denition may be extended to all successive
generations if sucient energy is available. In this sense, secondary ionization is very
Figure 5 Range distribution in nitrogen for 200-eV electrons obtained via the convolution method
at 110 eV [38]. The nal energy is about twice the ionization potential. See text for details.
important and it is a ubiquitous feature of all fast primary charged particles. Typically,
f25% of all ionizations are produced in secondary processes. Of course, experiments
count all ionizations, irrespective of whether they are primary or secondary.
The importance of total ionization yield derives from dosimetry and from providing
a standard against which other radiationchemical yields may be discussed [25]. For the
complete description of impact ionization, a vefold dierential cross-section is required in
principle; one for ejected electron energy and two each for the angular distributions of the
ejected electron and the incident particle. Such a detailed description is rarely needed. In
radiation chemical track structure, a cross-section doubly dierential in the energy and
angle of the ejected electron is sucient. Moreover, the Born approximation, against
which measurements and numerical calculations may be compared, starts to break down
as the incident energy is decreased. The onset for this breakdown occurs at a greater
energy if higher order dierential cross-sections are considered. A special issue of
Radiation Research [39] contains articles written by several experts on the experimental
and theoretical aspects of impact ionization, including higher order dierential cross-
sections. The calculation of the impact ionization cross-section for incident velocity v
proceeds, in the BornBethe approximation, in the same manner as that for energy loss
(see Sec. 2.2). In eect, energy loss is written as W
i
= E+I
I
, where E is the secondary
electron energy and I
I
is the ionization potential for the ith orbital from which the electron
is ejected. Combining the contribution from all the orbitals in the atom or molecule, the
dierential ionization cross-section for ionization may be given as follows [40].
dr=dE 4pa
2
0
z
2
R
2
=T
i
W
1
i
df=dW
i
ln4c
i
T=R 10
In Eq. (10), R is the Rydberg energy (13.6 eV), a
0
, the Bohr radius (0.053 nm), T=mv
2
/2,
df/dW
i
is the dierential dipole oscillator strength for the ionization process, and c
i
is a
dened additional contribution of the generalized oscillator strength [21]. Note that this
cross-section is basically given by the dipole oscillator strength, while there is a weak
dependence on the generalized oscillator strength through c
i
. Platzman has advocated the
use of the ratio of ionization cross-section to the Rutherford cross-section, Y(T,W) =(dr/
dE)(T/4pa
0
2
z
2
)(W/R)
2
, and its plot vs. R/W is called the Platzman plot [see Eq. (19) et seq.
of Chap. 3]. Here W=E+B
1
and B
1
is the lowest binding energy of the electron in
the molecular orbital. The usefulness of such a plot rests on: (1) lim
W!l
Z, the total
number of electrons, (2) autoionization and Auger processes show up as dips or peaks, (3)
for small values of E, Y resembles the shape of W(df/dW), and (4) in proton impact, a
peak is seen at ejected electron speed equal to the speed of the proton. Furthermore, the
area under the Platzman plot is proportional to the total ionization cross-section, the
constant of proportionality being T/4pa
0
2
R. Kim [40] has made repeated use of the Platz-
man plot in a careful analysis of secondary electron spectra, in some cases correcting some
experimental values. Another plot, (T/R)(dr/dE) vs. ln(T/R), called the Fano plot, is
useful in extrapolation and interpolation of experimental data. It approaches a straight
line at high T.
The above considerations need relativistic correction at vfc, which may be
performed in a straightforward manner. More importantly, Eq. (10) assumes that the
ionization process is direct, i.e., once a state above the ionization potential is reached,
ionization occurs with a certainty. Platzman [25] points out that in molecules, this is not
necessarily so and superexcited states with energy exceeding the ionization potential may
exist, which will dissociate into neutral fragments with a certain probability. For example,
in water in the gas phase, ionization occurs with a sharp threshold at the ionization
potential (I.P.)=12.6 eV, but only with an eciency of 0.4. Beyond the I.P., the ionization
eciency, determined by the ratio of ionization to the photoabsorption cross-section, varies
with the energy until f18 eV, beyond which it approaches unity [41]. In such cases, the
cross-section formula given in Eq. (10) must be suitably modied to account for the
ionization eciency. There is a very denite phase eect on the ionization eciency,
because of which the existence of superexcited states in liquid water has recently been
questioned [42]. The typical values of proton impact ionization cross-section in the gas
phase, for H, He,H
2
, N
2
, CO
2
, NH
3
, and CH
4
are 1.12, 0.93, 1.96, 5.33, 8.11, 4.62 and 6.84
A
2
, respectively, at 100 keV, and 0.19, 0.21, 0.38, 1.46, 2.13, 1.30, and 1.66, respectively, at 1
MeV. Rudd etal. [43] have given an empirical formula for the total ionization cross-section
due to a heavy ion at energy U, viz. r
t
1
=r
l
1
+r
h
1
, where r
h
(A
2
) =3.52(R/U)(A ln[1+U/
R]+B) and r
t
(A
2
) =3.52C(U/R)
D
. This form has the correct asymptotic behavior given by
the BornBethe cross-section at high energy. The parameters A, B, C, and D have been
tabulated, and a similar formula for incident electrons is also available. The corresponding
secondary electron spectrum involving some 10 adjustable parameters has been empirically
found to be very useful. It is discussed in some detail in Chap. 3 [Eqs. (29)(35)].
3.2. The Degradation Spectrum
The complexity of electrons of dierent energy and generation actually present in an
irradiated system, together with their primary counterparts, if dierent from the electron,
is represented by the degradation spectrum, which is dened to be the normalized energy
spectrum of these particles owing through the surface of a small cavity inside the
medium. Spencer and Fano [44] show that a convenient measure of this spectrum is given
by y(T
0
,T), such that y(T)dT is the total mean distance traveled by electrons of all
generations (primary, secondary, etc.) between energies T and T+dT, with T
0
being the
initial energy at unit ux. The degradation spectrum serves a purpose similar to the
distribution function in statistical mechanics, in the sense that the yield of any primary
species x is given by N
x
T
0
Nm
T
0
I
x
r
x
TyT
0
; TdT, where r
x
is the cross-section for the
production of x with an energetic threshold I
x
(e.g., for ionization). Note that y needs to be
evaluated only once for each initial energy, after which it may be used for all products.
Although y depends on T
0
, some approximate scaling property of the electron degradation
spectrum has been noted [45].
Calculation of the degradation spectrum has proved to be dicult in all but the
simplest cases of H, He, and H
2
, because of the lack of accurate energy-loss cross-sections
(mainly nonionizing) over a wide span of energy. Furthermore, to calculate the yield of a
particular species, its own production cross-section must be known over a wide interval of
energy, which is rarely available. In the continuous slowing down approximation (CSDA),
the contribution to the degradation spectrum of a single electron is the reciprocal of the
stopping power. Therefore after knowing the ionization cross-section and the electron
stopping power, one can compute the partial degradation spectrum generation by
generation. Finally, the total degradation spectrum may be obtained by summing up.
Such a procedure has been followed by Kowari and Sato [46] for gaseous water. Apart
from demonstrating the methodology, the actual results are of limited use because of
various dubious cross-sections used. More sophisticated methods employ the Spencer
Fano equation [45], or the Fowler equation [47]; however, the problem of accurate cross-
sections still remain in most cases. Another numerical approach by Turner et al. [48] relies
on Monte Carlo simulation. Their computed spectra show considerable dierence between
the gas and liquid phases of water, especially in the low energy region, which is a direct
consequence of the peculiar kinds of cross-sections used by them in these phases. One
feature is common to all electron degradation spectra. It has large values at the high
starting energy and also at very low energies. The former is attributed to low stopping
power and the latter is attributed to the accumulation of electrons of dierent generations.
Therefore the spectrum is expected to show a drop at some intermediate energy, often near
where the stopping power goes through a broad peak. It should be noted that, like the
stopping power and the range, the degradation spectrum also refers to mean values, and
considerable uctuation may be expected, especially at higher energies.
3.3. The W Value
The reciprocal of the ratio of the mean number of ionizations n
i
produced by the complete
absorption of a primary particle of energy T is dened as the (integral) W value. Ioniza-
tions produced by all secondary electrons are counted in it. A dierential, or track segment
x value, may be similarly dened, so that 1/x=(d/dT)(T/W). If W is independent of T,
so is x and vice versa. Generally, W depends weakly on T, unless the initial energy is very
low. Its dependence on the nature of the incident radiation (electrons, alpha-particles, etc.)
is also minor. These factors constitute the basis of dosimetry, by collecting and measuring
the total ionization. It also means that the Bragg curve, or the variation of total ionization
with incident particle energy, is a reliable measure of the relative stopping power. Thus the
W value is mainly a property of the medium, determined by the cross-sections of ioniza-
tion and of other nonionizing energy-loss processes. As such, the W value often depends
on the phase.
Platzmans [49] analysis for the W value may given as W = hE
ion
i+v
ex
hE
ex
i+hE
s
i,
where hE
ion
i, hE
ex
i, and hE
s
i are the average energies for ionization, excitation, and
subexcitation electrons, respectively, and v
ex
is the relative number of excitations to
ionizations. It provides a basis for understanding the insensitivity of W on particle energy,
because the quantities involved depend not so much on absolute cross-sections for
ionization and nonionizing energy loss, as it depends on their ratio.
An early theory of the W value was proered by Spencer and Fano [44], based on the
degradation spectrum. Another method, the Fowler equation, was employed by Inokuti
[47] for electron irradiation, based on the approximation that there is only one ionization
potential and that the ionization eciency is unity. These restrictions can be relaxed. The
main result of Inokutis analysis may be given as follows.
WT W
l
1 U=T
1
; where U EV I: 11
In Eq. (11), W
l
is the asymptotic W value at very high energy, I is the ionization potential,
U is a so-dened energy parameter, and EV is interpreted as the average energy transfer
in ionizing collisions where the ejected electron is subionization, i.e., incapable of further
ionization. Thus, U is the excess of EV over the ionization potential. An expression of
EVmay be given in terms of the dierential probabilities of ionization with energy loss
between E and E+dE, viz. EV m
2l
l
Edp
i
E; T=dEdE=m
2I
I
dp
i
E; T=dEdE, where these
probabilities are simply the ratios of the relevant ionization cross-sections to the total
energy loss cross-section. Eq. (11) impressively applies for various media over a wide span
of energy, except perhaps at very low energy.
Another numerical method devised by LaVerne and Mozumder [50] has been applied
to gaseous water under electron and proton irradiation. Considering a small section of the
track, the Wvalue due tothe primaryparticle only, maybe writtenas x
P
=S(E)/Nr
i
(E), where
S(E) is the stopping power, N is the molecular density, and r
i
(E) is the total ionization
cross-section at energy E. The number of secondary electrons produced, in all generations,
per unit track length is given byNm
e
m
I
dr
i
=dee=Wede, where W(e) is the integral W value
for electrons at energy e, dr
i
(e)/de is the dierential cross-section for producing secondary
electrons of energy e, and e
m
is the maximum secondary electron energy often well
approximated by (EI)/2. Combining, the dierential x value at electron energy E is given
by xE SE=Nr
i
m
e
m
I
dr
i
=deeW
1
ede. From this equation, the overall W value
may be calculated through integration by using the stopping power, ionization cross-
section, and the integral W values obtained at lower energies. A building-up principle has
been used by dividing the incident energy into several intervals, I3I, 3I7I, 7I15I, and so
on. In the rst interval, no secondary ionization is possible and x(E) = x
P
(E), although
an integration is necessary to compute W(E). In subsequent intervals, the W(E) values of
previous intervals may be used together with stopping power and ionization cross-section
obtained either from experiments or tabulations. By careful analysis of experiments and
compilations, LaVerne and Mozumder [50] made the following conclusions. (1) Various
experiments on the ionization cross-section are basically in agreement with each other, but
those on the excitation cross-section are not, which is the major source of uncertainty in
the calculation of W value. (2) For electron irradiation, an asymptotic W
l
is reached at 1
keV, but the computed value (34.7 eV) exceeds measurement [51] (29.6 eV) by 15%,
attributable to errors in inelastic cross-sections. (3) For proton irradiation, W
l
is reached
at 500 keV and the computed value (28.9 eV) is in good agreement with experiment [51]
(30.5 eV). In both cases, x
P
greatly exceeds W, underscoring the importance of secondary
ionization.
Cole [52] measured the W value in air for electron energies from 5 to 20 eV, while the
electrons were completely absorbed in the ionization chamber. Later, Combecher [53]
extended the measurements of W(E) to several gases including water vapor. Fig. 6 shows
the variation of W(E) with electron energy in water vapor, as measured by Combecher,
Figure 6 Comparison of experimental (. . .) variation of integral W value for water vapor [50] with
theoretical calculation ( ___ ) and with an empirical model (- - -). Note that the accuracy of the
theoretical calculation is limited by an inherent error in inelastic collision cross-sections, while in
the empirical model, U = 12.6 eV has been adjusted to obtain best agreement with the experiment.
The experimentally determined asymptotic limit, W
l
= 29.6 eV is indicated by the arrow.
and compares it with the calculation of LaVerne and Mozumder and also with Inokutis
result, obtaining U = 12.6 eV, close to the ionization potential, for best adjustment.
The eect of condensation on the W value has been treated elsewhere in some detail
[54]. Except for liqueed rare gases, where the W value in the liquid is somewhat less than
that in the gas phase, there is an operational problem in the denition of Wthus
requiring long extrapolation. In some hydrocarbons such as cyclohexane, the admittedly
long extrapolation of scavenging yield gives a W value not far from the level obtained in
the gas phase (f26 eV for cyclohexane). In most polar liquids, W
liq
(22 F 1 eV for water)
is considerably less than W
gas
(31 F 1 eV for water). The exact reason for the additional
yield of ionization in the liquid phase is not clear, but a signicant contributing factor
could be the conversion of excited states into ionization by interaction with neighboring
ground state molecules in the liquid phase.
As for the stopping power and the degradation spectrum, the W value is also a mean
quantity and ionization uctuation is expected because of the various ways a deposited
energy can be partitioned into ionizing and nonionizing events. The Fano factor represents
such uctuations, and it is dened as the ratio of mean square uctuation of ionization to
the average number of ionizations, i.e., F = (hn
2
i
ihn
i
i
2
)/hn
i
i, where n
I
is the number of
ionizations detected in a sample. For a Poisson distribution, F = 1; for other distributions,
it is <1. For the operation of a radiation detector, a smaller Fano factor means better
energy resolution. With solid state detectors using Si or Ge, Fano factors of f0.05 can be
achieved. Other liqueed rare gas detectors have Fano factors in the range f0.1 to f0.2.
4. CONCLUSION
In this chapter, we have attempted to describe the interaction of fast charged particles with
matter from the point of view of the incident radiation, i.e., basically radiation physics. We
have discussed such topics as energy transfer from incident radiation to ionized and
excited states of medium molecules, as well as theories of stopping power and secondary
ionization eects. In many of the succeeding chapters, topics which are more chemical in
nature will be found, i.e., the response of the matter receiving the transferred energy. In
this sense, this chapter may be considered as preparatory groundwork for the succeeding
contributions.
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FL: CRC Press, 1991, chaps. 2 and 3.
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3. Fano, U. Annual Review Nuclear Science 1963, 13, 1.
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Interscience: New York, 1969, chap. 1.
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6. Land, L.L.; Hanrahan, R.J. In Environmental Applications of Ionizing Radiation; Cooper, W.J.;
Curry, R.D.; OShea, K.E.; Eds.; John Wiley: New York, 1998, chap. 24.
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York, 1968, 4392.
9. Kellerer, A.M.; Rossi, H.H. In Proceedings of 2nd Symposium on Microdosimetry, Ebert, H.G.,
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10. Fano, U. Comparative Eects of Radiations; Burton, M.; Kirby-Smith, J.S.; Magee, J.L., Eds.;
John Wiley: New York, 1960, 1421.
11. Mott, N.F. Proc. Roy. Soc. A 1930, 126, 79.
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13. Fano, U. Revs. Mod. Phys. 1992, 64, 313.
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17. Bohr, N. Kgl. Dan. Vied. Selskab. Math.-Fys. Medd. 1948, 18, 9.
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20.
26. Nicholls, R.W.; Stewart, A.L. In Atomic and Molecular Processes, Bates, D.R., Ed.; Academic
Press: New York, 1962, 47.
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3
Ionization and Secondary Electron Production
by Fast Charged Particles
Larry H. Toburen
East Carolina University, Greenville, North Carolina, U.S.A.
1. INTRODUCTION
From the rst studies of cathode rays leading to the discovery of the electron in 1897 by
J.J. Thomson, there has been intense interest in understanding the characteristics of the
interactions of fast charged particles with matter. Early studies of electron impact
excitation of gases led to important constraints on evolving models of atomic structure
as well as contributing to the discovery of x-rays and natural radioactivity. With the dis-
covery of energetic alpha particles emanating from natural radioactivity, Rutherford and
his coworkers were able to investigate heavy charged-particle scattering in materials and
gain new insights into the physical nature of atomic structure and of charged particle
scattering. These studies also stimulated new questions regarding the mechanisms of ener-
gy loss by heavy charged particles in matter.
The rst decades of the 20th century saw great advances in our knowledge of charged
particle interactions with matter. With the discovery of nuclear ssion came enhanced
availability of radionuclides and nuclear radiations, including fast ssion fragments, neu-
trons, alpha and beta particles. Coincidently, with the development of nuclear technology
came the need to better understand the physical, chemical, and biological interactions of
radiation with matter. The potential exposure of materials and people to nuclear radiation
emphasized a need to understand the underlying mechanisms leading to damage by ra-
diations of dierent types. The early part of the 20th century was also a period of rapidly
expanding technology enabling one to produce and accelerate electrons and ions and to
explore new applications of radiation in science and industry. Understanding of the in-
teraction of radiation with matter has important applications in numerous research and
applied elds of endeavor, including the sterilization of food and medical instruments,
medical diagnosis and treatment of disease, and developments of nuclear energy and radio-
active waste management (see the Preface and Chap. 26). In this chapter, we will explore
the fundamental mechanisms for the interaction of fast charged particles with matter, with
focus on their signicance to the subsequent chemistry initiated by the absorption of ioniz-
ing radiation.
Ionizing radiation, as the term implies, denes those radiations that interact with
matter by the production of charged particles, namely electrons and residual positive ions.
Energetic electromagnetic radiation, i.e., x-and g-rays, interact with matter predominately
via production of photoelectrons and Compton electrons, and, if the photon energy is
greater than about 1 MeV, the production of electronpositron pairs. These primary
electrons can have a broad spectrum of energies from subexcitation, or very slow
electrons, to what are generally called fast charged particles. Here fast implies particles
with velocities much larger than bound electrons of the medium. As we will see, electrons
and fast heavy charged particles, e.g., protons and alpha particles, predominantly interact
with the bound electrons of the medium producing secondary electrons via target
ionization. For completeness, we note that the interaction of neutrons with matter also
leads to local energy deposition by charged particles; neutrons primarily interact through
elastic nuclear scattering, resulting in the production of energetic recoil charged particles
characteristic of the absorbing medium. Ionization resulting from the slowing of energetic
ions and electrons leads to the production of charged and/or neutral molecular fragments,
reactive radicals, and other excited chemical species that foster subsequent chemical
reactivity in the absorbing medium. Because all ionizing radiation leads to electron
production, the dierent chemical yields observed for dierent types of radiation must
depend on the detailed spatial distributions of initial events produced in the physical
process of electron slowing. All radiation-induced chemistry begins with the stochastic
physical processes involved in energy deposition by charged particles.
Investigation of the interactions of charged particle with matter has traditionally
been viewed as comprised of studies falling into two fundamental classes: Class I studies
focus on the fate of the particle, and class II studies focus on the fate of the absorbing
medium [1] (cf. Sec. 2.1.2). The former is most commonly represented by the studies of
charged-particle stopping powers, whereas the latter includes studies of media quantities
such as the average energy per ion pair (W value), or more specically, the fundamental
processes of ionization and excitation that contribute to spatial structure in the patterns of
energy deposition. In the following, we will rst discuss the stopping of fast charged
particles through the general theory of stopping power, its strengths and limitations, and
then look more closely at the individual processes that contribute to energy loss and are
incorporated within the general concepts of stopping power.
2. STOPPING POWER
When a fast charged particle passes through matter, it loses energy by interactions in-
volving momentum transfer to the bound electrons of the media. If the particle slows to
the point that insucient momentum can be transferred to excite these bound electrons to
vacant states, energy loss will then occur through elastic collisions with the target atom, or
the target matrix, as a whole. This latter energy-loss mechanism, termed nuclear scat-
tering, dominates for ion energies less than a few keV per atomic mass unit (keV/u), i.e.,
for ions near the extreme end of their range. For high-energy or fast particles, i.e., particles
with velocities large relative to the velocities of bound electrons, inelastic collisions involv-
ing electron excitation and ionization dominate the energy loss process. At intermediate
energies, the competition between elastic and inelastic processes depends on the atomic,
molecular, and condensed-phase properties on the absorbing medium and, for heavy
charged particles, additional channels of electron capture and loss can become important
mechanisms for energy loss.
Stopping power has been the subject of study for more than a century beginning with
the pioneering work of Thompson and Rutherford. With the discovery of nuclear ssion
and subsequent developments in accelerator technology, energetic heavy ions with rel-
atively high energies became readily available and the experimental and theoretical study
of stopping power made steady advances (see, e.g., Refs. 24; and the excellent review of
stopping power for protons and alpha particles published in 1992 by the International
Commission on Radiation Units and Measurements [5]). These studies have been an im-
portant means of testing our theoretical understanding of charged particle interactions
with matter as well as being of practical use in many scientic and applied elds of ap-
plication. Because stopping power can be measured with relatively high accuracy using
modern charged particle detection techniques, of order 1%, we can rene our theoretical
understanding of the penetration of charged particles in matter to a high degree by com-
parisons of theoretical and experimental results.
Many textbooks describe derivations of the dominant features of energy loss incor-
porated in stopping power (see, e.g., Refs. 6 and 7). The primary energy loss mechanism
for a fast charged particle is the interaction between the coulomb charge of the moving
charged particle and that of electrons of the absorbing medium. This interaction is gen-
erally approximated as a transverse momentum impulse delivered to the bound electron by
the coulomb charge of the passing charged particle integrated over the interaction times
and impact parameters. A detailed derivation of stopping power has been presented else-
where (see Sec. 2.2). The important concept from stopping power is that the energy loss by
the fast particle is to the bound electrons of the medium. Increasingly complete theories of
stopping power, from detailed rst-order approximations to full quantum calculations, are
described in a number of reviews (see, e.g., Ref. 5 and references therein). The expression
for the mass stopping power for a charged particle of velocity v and atomic number z in a
medium of atomic number Z and atomic mass A is given in ICRU report 49 [5] as
1
q
dE
dx

0:30708
b
2
z
2
Z
A
Lb
MeV cm
2
g
_ _
; 1
where L(b) is obtained from the sum of three terms
Lb L
0
b zL
1
b z
2
L
2
b: 2
The parameters in Eq. (1) illustrate the primary dependence of stopping power on the
square of the projectile charge z, the velocity of the projectile b, and the density of target
electrons Z/A. The mean excitation energy I, a major target parameter, is incorporated in
the rst term of L(b) given as
L
0
b
1
2
ln
2mc
2
b
2
W
m
1 b
2
_ _
b
2
lnI
C
Z

d
2
3
with
W
m

2mc
2
b
2
1 b
2
1 2m=M1 b
2
1=2
m=M
2
1
: 4
Equation (3) incorporates relativistic eects, eects of target density, and corrections to
account for binding of inner-shell electrons, as well as the mean excitation energy; C/Z is
determined from the shell corrections, d/2 is the density correction, W
m
accounts for the
maximum energy that can be transferred in a single collision with a free electron, m/M is
the ratio of the electron mass to the projectile mass, and mc
2
is the electron rest energy. If
the value in the bracket in Eq. (4) is set to unity, the maximum energy transfer for protons
is only overestimated by 0.1% at 1 MeV, and by 0.23% at 1000 MeV [5]. The shell cor-
rections are included to reect the fact that, as the ion velocity decreases, the assumption
of the particle being fast can fail for interactions involving inner shell electrons; thus
contributions from inner-shell electrons decrease and corrections to the Bethe theory are
required. The density correction accounts for the fact that a moving charge tends to po-
larize the transport medium thereby reducing the stopping power slightly. The shell correc-
tions are predominately a low-energy phenomenon whereas the density correction occurs
for high energies. The second term in Eq. (4) is required to account for the observation
that stopping power for negatively charged particles is smaller that that for positively
charged particles at the same velocity. This correction is often called the Barkas correction
after his measurements determined that the range of negative pions was somewhat larger
than that for positively charged pions. This correction is often simply referred to as the z
3
correction because it depends on the cube of the particle charge. The last term in Eq. (4) is
needed to bring agreement between the rst-order theory of Bethe and a full quantum
mechanical result of Bloch valid for high-energy particles. All of these additional cor-
rection factors have come about because of approximations made in the theoretical
development of stopping power theory and because the ability to make accurate measure-
ments of stopping power enables one to identify subtle dierences between theory and
experiment. The reader is directed to ICRU Report 49 [5] and to Chap. 2 for details in-
cluding the full description of stopping power and the terms identied in Eqs. (1)(4).
The most signicant target parameters for the determination of stopping power
are the electron density and the mean excitation energy I found in the logarithmic term of
Eq. (3). The mean excitation energy is related to the oscillator strength distributions of the
absorber and is, in general, determined from tting experimental data after all corrections
to the rst-order theory have been included. Once values of I have been determined for
elemental constituents of molecules or materials, one can obtain I for a composite
material by
lnI
i
n
i
Z
i
lnI
i
i
n
i
Z
i
; 5
where n
i
, Z
i
, and I
i
represent the atomic concentration, the atomic number, and the mean
excitation energy of the ith component of the target molecule or compound. This tech-
nique has been extensively used by Porter et al. (see Refs. 59 and references therein) to
determine stopping power for composite materials such as mylar and Al
2
O
3
. It is this
formula for determining the mean excitation energy for compounds from individual ele-
ments that also leads to additivity among stopping powers. One can obtain the stopping
power for a compound from a weighted sum of the stopping powers of the constituent
elements.
The discussion of stopping power above has focused on interactions by bare fast
charged particles. As fast positively charged particles slow, they can capture and sub-
sequently lose electrons; thus they can move through material with a somewhat reduced
average charge. Electrons bound to the projectile screen the projectile charge, reducing
the interaction strength, thereby reducing the stopping power. This reduction is generally
incorporated in stopping power theory by assuming a reduced value of the projectile
charge, z
e
in Eq. (1). This reduced eective charge is dened as the square root of the
ratio of the stopping power for the screened projectile to that of the bare projectile. It must
be emphasized that this eective charge of stopping power theory is not the same as the
average charge state of the moving ion. The dierence exists because interactions leading
to energy loss occur at a somewhat dierent range of impact parameters than those as-
sociated with the capture and loss of electrons, and the screened nuclear charge of the
moving particle is strongly dependent on the impact parameter. The eective charge of
stopping power theory is an average over all individual stochastic events contributing to
the stopping power, each of which is weighted by an eective charge z
e
(E) that depends
on the energy loss E occurring in that event [10]; this is discussed in more detail later in this
chapter. The dierence between the eective and average charge is illustrated in Fig. 1
where the eective/average charge of a proton is plotted vs. the ratio of the projectile ve-
locity to the bound target electron velocity. Data shown in Fig. 1 were derived from stop-
ping power measurements of Yarlagadda et al. [11], the eective charge formula of Barkas
derived for stopping power [12], and the average charge obtained from charge-transfer
measurements [13]. Note that only for large velocities of the projectile, where the projectile
in essentially bare, are the average and eective charges the same.
The importance of the various interactions that contribute to stopping power is
illustrated for a range of energies involved in stopping a fast proton in Fig. 2. These data,
taken from the compilation by Uehara et al. [14], clearly illustrate the importance of target
ionization as the leading contributor to energy loss by protons: ionization by protons
occurs at the higher energies and ionization by H
o
at the lower energies. Energy loss
processes involving electron capture by protons and electron loss by H
o
are also important
at particle energies less than about 100 keV; or energies less than a few hundred keV/u for
heavier charged particles (not shown). Excitation is observed to be a small contribution to
Figure 1 Comparison of the eective charge of a proton obtained from the work of Yarlagadda et
al. [11], the eective charge obtained from the empirical formula of Barkus [12], and the average
charge
_
q determined from charge transfer cross section tabulated by McDaniel et al. [13]. The solid
line is a guide through the data of Yarlagadda et al.
total energy loss at all energies and never exceeds about 10% even at its maximum con-
tribution. However, it should be emphasized that contributions to energy loss attributed to
excitation are relatively uncertain having been estimated from an empirical model based
on limited data [15]; there is little actual data available for excitation by protons or other
charged, or neutral, heavy particles.
There are also many channels of energy loss that have not been included in Fig. 2
because they either contribute only a small amount to the total energy loss, or because we
lack reliable data to assess their contribution. However, it is possible that the special
nature of some of these less-probable interactions might have weighted important in the
evolution of subsequent chemical reactions. For example, multiple ionization of the target
atom or molecule involving the simultaneous ejection of two or more electrons in a single
event has been documented for ion collisions with rare gas atoms (see, e.g., Refs. 16 and
17, and references therein). Although these interactions are relatively rare events, the
emission of two or more electrons correlated in time and space might have important
consequences on the subsequent chemistry [18]. Unfortunately, there are few data avail-
able to guide our understanding of the relevance of such interactions in chemical systems.
Energy loss by ionization of inner-shell electrons is also missing from Fig. 2. Ionization of
the K-shell of oxygen in the water molecule happens only rarely compared to outer shell
interactions, but inner shell ionization followed by Auger electron emission can lead to
multiply ionized targets with unique chemical properties. When estimating the importance
of energy deposition events, the subsequent chemical reactions under consideration can
oer the dening criteria as to whether the rare events have weighted importance. Also
lacking from Fig. 2 is information on the contributions leading to dierent molecular end
points such as dissociative excitation, dissociative ionization, autoionization, etc. Surely
such processes occur and are relevant to understanding the subsequent chemical activity
Figure 2 Contributions to the total stopping cross section S
T
from ionization r
i
by H
+
and H
o
,
electron capture r
EC
by H
+
, electron loss r
EL
by H
o
, and excitation r
EX
by protons in water. The
data are from a compilation by Uehara et al. [14]. The ICRU recommendation S
T
-ICRU is from
Ref. 5.
following energy deposition by fast charged particles, but again there is little information
regarding these processes for heavy charged particles that can be used to dene their im-
portance. On the other hand, a great deal is known regarding the interactions of electrons
with molecules and the production of various nal molecular states (see, e.g., Ref. 19), this
will be addressed below.
The discussion of stopping power presented above was not meant to be rigorous, but
to illustrate that extensive study has been devoted to both experimental and theoretical
features of stopping power, and that these results provide benchmarks against which
stochastic models of energy loss can be tested. Stopping powers are known with extreme
accuracy and any alternative full description of the stopping of charged particles, e.g.,
stochastic trackstructure models, MUST be consistent with known stopping powers (cf.
Chap. 4). Second, we note that the stopping power gives essentially no information on the
fate of the energy deposited, it is a particle-centered parameter. Thus stopping power, no
matter how accurate, is of limited use in generating detailed information as to what chem-
istry might follow energy deposition by ionizing radiation.
To model the potential chemical reactions that might follow energy deposition, it is
necessary to better understand the local spatial characteristics of the initial products of
ionization and excitation, e.g., are products within reaction distances, is recombination
likely prior to chemical reaction, etc. This information is contained in the collection of
many small events clustered along the path of the particle, and to understand the sub-
sequent chemistry, one must describe the basic interactions that accompany energy depo-
sition on a spatial scale relevant to the reaction of interest (see Chap. 4). For fast protons
and electrons, the important fundamental interactions are fairly straightforward. Fast ions
deposit about 90% of their energy in ionizing collisions with about 10% of the energy
deposited as excitation. Thus if we understand ionization, the production and slowing
down of secondary electrons, we can understand how most of the energy is deposited; but
be aware that determining the fate of the energy in the absorbing medium requires in-
formation on the dierential ionization cross sections. For fast electrons and other bare
particles, e.g., protons and alpha particles, there are many sources of experimental and
theoretical data; the same is not true for heavier particles or for slow particles that carry
bound electrons.
3. W VALUES
As has been emphasized, energy deposition by energetic charged particles is a stochastic
process involving large numbers of events, each event involving small quantities of energy
transfer. All detection devices used in the laboratory provide some form of averaging,
whether we are counting numbers of target ions created, the number of electrons or
photons emitted, yields of radicals, etc. Stopping power is the stochastic average over all
energy loss processes of the projectile. On the other hand, the W value is a media-centered,
class II, quantity representing the average energy required to produce an ion pair by the
passage of a charged particle (cf. Sec. 2.3.3). Thus W is given by
W
E
J
; 6
where E is the total amount of energy absorbed in a volume of gas and J is the total
number of ions produced in that volume. This quantity has been, as was stopping power,
the subject of extensive investigation for more than a century (see, e.g., Ref. 20 and
references therein) and provides a media-centered quantity of relatively high accuracy for
testing of quantities obtained from stochastic averages of energy deposition events. As was
the case for stopping power, this average provides little information on the actual events
produced during the absorption of radiation energy and thereby is of little guidance in
estimating the chemical reactions that might follow energy deposition. On the other hand,
the study of W values provided the rst approach to the analysis of energy deposition in
terms of a description of the target as a mixture of oscillators whose frequencies are
characteristic of the spectral absorption frequencies of the target [21]. In addition, as an
accurately measurable target property, it provides another benchmark that any stochastic
calculation must return when averaged over sucient numbers of interactions.
4. CHARGED PARTICLE TRACK STRUCTURE
Both stopping power and W values give averages over all energy deposition events making
up the path of the charged particle in the medium of interest. As averages, they tell us little
of the individual processes that can aect the subsequent chemical reactions initiated by
the absorption of ionizing radiation. Historically, the term linear energy transfer (LET)
was dened to help describe information on the local densities of energy transferred to
the medium per unit length of particle track (class II), as distinct from the energy lost
dened by stopping power (class I). This was a rst step in better understanding the eect
of local energy density on chemical yields. The quantity LET diers from stopping power
in that excitation or ionization resulting in emission of photons that might carry energy
from the local area of interest are not included in LET. However, the use of LET as a
radiation parameter has been found inadequate for many applications because particles of
the same LET can produce quite dierent yields of chemical products [22]. An extension of
the LET concept to dene a restricted LET
D
to either (1) restrict the energy deposited to be
within a certain radius of the charged particle track, or (2) to restrict the magnitude of the
energy deposited in any single event, was made to further investigate the eects of local
energy deposition. These denitions both eectively restrict the energy of secondary elec-
trons that are included in the analysis of events along the charged particle track. Although
restricted LET has had some success in radiation biology [23,24], it has found little ap-
plication in radiation chemistry.
The importance of the stochastic nature of energy deposition in nonhomogeneous
reaction kinetics was emphasized in early studies of molecular yields by Mozumder and
Magee [25,and,referentherein,therein]. They realized that the density of energy deposition
would randomly vary along a charged particle track and that these variations would be a
function of the primary electron energy. Their rst eort to incorporate the statistical
distribution of energy along charged particle tracks was to dene regions called spurs in
which energy deposition of up to 100 eV would occur stochastically distributed along a
particle track. Later, these entities were augmented with regions called blobs, in which
energy depositions from 100 to about 500 eV were dened, and with short tracks, which
would include energy deposition from 500 eV to about 5 keV. These entities represent
regions of signicantly dierent chemical reactivity brought about by the statistical nature
of energy deposition. The probabilities for energy deposition associated with each of these
track entities were either determined analytically or by the use of Monte Carlo techniques.
Their estimates of the frequency of such entities were somewhat crude at the time owing to
the lack of detailed information on the interaction of electrons in the medium of interest,
but their results were successful in illustrating the importance of spatial variations in en-
ergy deposition on the subsequent radiation chemistry. These pioneering studies have led
to a large number of new Monte-Carlo-based models of energy deposition that maintain,
to varying degrees, the stochastic nature of the energy deposition process (see, e.g., Sec. 4.4
and Refs. 2634). The basic premise in the application of charged particle track structure
models is that one must include accurate information on the initial spatial distribution of
events involving ionization and excitation occurring along the path of a charged particle if
accurate models of the subsequent chemistry are to be developed. A motivating force in
the development of these stochastic models has been their application in radiation biology
where the chemistry and biochemistry following energy deposition by ionizing radiation
ultimately leads to biological damage.
To develop complete descriptions of the process of energy deposition along a
charged particle track requires an extensive database of interaction cross sections for the
primary particle as well as those initiated by secondary electrons produced in ionizing
collisions. Some of the more important interaction processes for heavy charged particles
were shown in Fig. 2. Not explicit in the depiction of cross sections shown in Fig. 2 is the
importance of dierential cross sections for electron production (ionization) that enable
one to derive a three-dimensional description of the spatial patterns of energy deposition.
To develop detailed models of the spatial characteristics of charged particle tracks requires
detailed information on the energy and angular distributions of electrons produced by
primary electrons or ions, along with similar cross sections for all secondary electrons. In
the case of fast heavy charged particle track structure, dierential cross sections for
electron production for partially screened projectile nuclei are also needed as they capture
electrons during slowing. The initial positions of all products of excitation, ionization,
and, where appropriate, charge transfer, will determine whether secondary electrons and
the corresponding residual media ions will recombine or proceed to initiate chemical
reactions.
In the following sections, the interaction mechanisms contributing to the stochastic
description of the energy loss process are discussed, as well as the trends in cross sections
as a function of the incident particle energy and charge state. To develop a full stochastic
description of a charged particle track useful for chemical and radiological applications, it
is important that the available cross section data fulll what has been called by Inokuti
[35] as the trinity of requirements; that the cross sections be absolute, correct, and
comprehensive. Where gaps in data exist, one must often use theoretical techniques to
bridge the gaps, in which case it is important to understand the limitations of the theories
and/or models being used and to strive to test the methodology with experimental data
wherever possible.
5. IONIZATION
The primary mechanisms for energy loss by ionizing radiation lead to ionization of the
atoms and molecules of the absorbing medium. The subsequent slowing of the electrons
from these primary ionizing events leads to the spatial relationships among the nal
physical products, e.g., ions, excited states, molecular fragmentation, etc., that are of
utmost importance to subsequent chemical reactivity. For suciently fast ions and
electrons, there are many similarities in the interaction process and some obvious dier-
ences. Electrons lose their energy primarily through coulomb interactions with bound
target electrons, in much the same way as heavy ions. However, electrons can lose all their
initial kinetic energy in a single collision with a bound electron whereas a heavy ion is
restricted to a maximum energy loss to a free electron E
max
given by
E
max

4m
1
m
e
m
1
m
e
2
E; 7
where m
1
is the incident particle mass, m
e
is the electron mass, and Eis the energy per atomic
mass unit u of the incident particle. Furthermore, electrons can undergo large angle scatter-
ing in collisions with media electrons, leading to extremely torturous paths, whereas heavy
ions move in a relatively straight line until very near the end of their range. For heavy ions
or neutral particles with energies less than a few keV/u, elastic scattering from the atom as
a whole, referred to as nuclear scattering, can dominate energy loss. At the other extreme,
very fast electrons can also lose energy by emission of radiation, bremsstrahlung, if they are
abruptly accelerated in collisions with target nuclei. The ratio of energy loss by radiation,
(dE/dx)
Rad
relative to that by ionization and excitation (dE/dx)
Col
is given approximately
by
dE=dx
Rad
dE=dx
Col
ZE
800
; 8
where Z is the atomic number of the target nucleus and E is the electron energy in MeV.
Slowing in water, Z c 8, a 10-MeV electron would lose somewhat less than 10% of the
energy loss per unit path length via radiation. In principle, heavy charged particles can also
lose energy through radiation; however, the probability of radiative energy loss is propor-
tional to the inverse of the square of the mass of the accelerated charge. Thus the probability
of radiative energy loss by a proton is a few million times smaller than that for an electron,
and for heavier ions the probability of radiative energy loss is even smaller.
Both electrons and heavy charged particles lose energy by coulomb interactions with
target electrons in basically the same manner. Collisions can be divided into two general
categories, those representative of distant, or soft, collisions and those characteristic of
close, or hard, collisions. For soft collisions, the energy transfer can be described as
occurring essentially with the entire atom or molecule leading to excitation of bound and
continuum states of the target. In hard collisions, the energy is directly transferred to a
bound electron in close knock-on collisions. Soft collisions resemble excitation and
ionization produced by photons; that is, the moving charged particle can be viewed as the
source of a continuum spectrum of photons with excitation and ionization of the target
produced by virtual photon exchange to the oscillators of the target. Thus character-
istics of soft collisions are similar to photo-excitation resulting in ejected electron spectra
determined from the oscillator strengths of the target and with angular distributions of
ejected electrons exhibiting dipole-like characteristics. On the other hand, the character-
istics of hard collisions are normally described by binary-encounter models of momentum
and energy transfer. Models of excitation and ionization also dier for electron and heavy
charged particle impact because electron exchange must be included in models for incident
electronsthis occurs because of the indistinguishability of incident and ejected electrons.
Ionization models specic to electron and heavy particle impact will be independently
discussed in the following sections of this chapter.
5.1. Ionization by Electrons
The fundamental mechanisms through which electrons interact with atoms and molecules
have been reviewed is detail by several authors; for additional details, see Ma rk et al. [19],
ICRU Report 55 [36], and references therein. Fast electrons predominantly interact via the
coulomb force with the bound electrons of the medium resulting in ionization, i.e., leading
to formation of free electrons and residual positive ions. The residual ions can be left in
any of a wide variety of nal states ranging from their ground ionic state, to states
resulting from simultaneous ionization and excitation, and/or dissociation of molecular
constituents of the target material. The interaction of a primary electron e
p
with the
diatomic molecule AB can precede via many channels, e.g., ionization can occur by any of
the following reaction pathways
e
p
AB !
AB
e
p
e
s
single ionization 9:1
AB
n
ne
s
e
p
n times multiple ionization 9:2
AB** e
p
! AB
e
p
e
s
autoionization 9:3
AB
* e
p
e
s
! Ionization plus !
A
B e
p
e
s
fragmentation 9:4
AB
2
e
p
2e
s
autoionization 9:5
AB
e
p
e
s
hm radiation 9:6
A
B e
p
e
s
dissociative ionization 9:7
A
e
p
ion pair formation 9:8
where e
s
is the secondary, or ionized, electron. For fast electrons, the most probable
reaction is that described by Eq. (9.1) with ionization occurring predominately with
valence electrons; however, in general, ionization can involve electrons bound in either
inner or outer electronic shells of the molecule or constituent atoms. There are also a
number on nonionizing channels that can be excited by an incident electron. These include
e
p
AB !
AB* e
p
simple excitation 9:9
A B e
p
neutral dissociation 9:10
A* B e
p
dissociation into excited neutrals 9:11
AB
electron attachment 9:12

A
B dissociative attachment 9:13

where the last two are most likely to occur for very low energy electron impact.
For collisions involving fast electrons, most of the relevant reactions given by Eqs.
(9.1)(9.13) occur with the primary and secondary electrons leaving the target molecule
promptly, in about 10
16
sec. One the other hand, autoionization and dissociative ionization
channels can result in a secondary electron being delayed relative to the primary, and in
the case of resonant electron attachment, there may be a measurable delay in the exit of the
primary electron. These processes are described in considerable detail by Ma rk et al. [19].
Total Cross Sections
Conceptually, the cross section is used as a measure of the probability of interaction
between charged particles (and energetic neutrals) and atomic and molecular targets.
The concept of a cross section can be dened by considering a beam of fast particles
traversing a media of suciently low density that there is a negligible probability of one of
the particles in the beam making more than one interaction. Under these conditions, the
number of interactions N is proportional to the number of incident beam particles passing
through the target N
o
, the number of target particles per unit volume n, and the length of
beam path through the target material L. Mathematically, this can be described under
these conditions as [36]
N N
o
nLr; 10
where r is the constant of proportionality, i.e., the probability of interaction. From the
dimensions of the parameters in Eq. (10), we note that r has units of area and we call this
measure of the probability of interaction the cross section. We hasten to note that this is
not a physical size of the target, but an area representing the target for the particular type
of event under consideration.
Numerous reviews of interaction cross sections for elastic and inelastic collisions
have been published for electron impact with atoms and molecules for electron energies
from a few meV (milli-electron volts) to a few keV (see, e.g., Secs. 4.2 and 4.3, as well as
Refs. 19 and 36, and references therein). For fast electron impact, simple ionization and
electronic excitation represent the most likely avenues of energy loss, with ionization
occurring in about 90% on the interactions. This is illustrated in Fig. 3, where recom-
mended values of inelastic and elastic cross sections presented by Ma rk et al. [19] are
shown for electron impact excitation of water molecules. Here r
T
is the total interaction
cross section determined as the sum of cross sections for elastic and inelastic processes.
The inelastic channels shown in Fig. 3 include the vibrational modes r
v1
(the bending
mode with threshold 0.198 eV), r
v2
(sum of two stretching modes with thresholds 0.453
and 0.466 eV), and r
v3
(a lump-sum of other vibrational excitation modes including higher
hormonics and combinational modes with an assigned threshold of 1 eV). The electronic
excitations r
e1
and r
e2
are shown with threshold energies of 7.5 and 13.3 eV. In addition to
excitation, the open circles show contributions to inelastic energy loss from ionization for
incident electron energies from near the ionization threshold to 150 eV, and the closed
circles represent ionization energy losses for electron energies from 50 to 1000 eV; these
data are attributed to Djuric et al., and Bolorizadeh and Rudd, respectively, and were
taken from the review by Ma rk et al. [19].
From the asymptotic high-energy behavior of the excitation cross sections shown in
Fig. 3, one observes, as discussed above, that the primary means of energy loss for electron
energies greater than 1 keV will be target ionization (
f
90%). Of course, at very high
energies, e.g., many MeV, bremsstrahlung will become an important factor in the energy
loss by electrons; as was also noted above, energy loss by bremsstrahlung can reach nearly
10% of the total energy loss for electrons of 10 MeV in water.
It should be emphasized that the data shown in Fig. 3 do not provide information on
the fate of the excited or ionized molecule; these data constitute a sum over nal molecular
states. Generally, measurements of excitation and ionization cross sections for fast
electrons do not provide information on subsequent target relaxation modes. However,
this information is often available from separate measurements that focus on state-selected
partial cross sections and molecular fragmentation [19].
The total cross sections shown in Fig. 3 can be used to provide information on the
relative distances between collisions, i.e., the mean free path of an electron moving in the
target medium. The mean free path between collisions is simply obtained from the re-
ciprocal of the cross section 1/r
f
, where f designates the interaction channel of interest. For
example, the mean free path for ionization would be 1/r
i
and would be quite dierent from
the mean free path for excitation 1/r
ex
. The total ionization, or total scattering, cross
section provides information on the distance between collisions, but gives only limited
information of the spatial distribution of products produced along the electron track. A
full three-dimensional distribution of events requires the additional detail provided by
energy and angular dierential inelastic and elastic scattering cross sections for both the
primary and secondary electrons. Obviously, if dierential cross sections are available,
total cross sections can be obtained by integration over the appropriate variables.
Historically, measurements of total ionization cross sections have been obtained from
both the total charge measurements and by the integration of measured dierential cross
sections. For a review of the dierential cross section measurements, see Refs. 19 and 36,
and references therein.
Dierential Ionization Cross Sections for Electrons
Dierential ionization cross sections, dierential in ejected electron energy and emission
angle, were the subject of intense study during the 1970s and 1980s. Considerable progress
was made in both experimental and theoretical methodologies needed to describe dier-
ential cross sections; these have been reviewed in IAEA TECDOC-799 [19] and ICRU-
Figure 3 Inelastic and elastic cross sections for electron impact excitation of the water molecule;
the data are from the review by Ma rk et al. [19]. The total interaction cross section r
T
was
determined from the sum of cross sections for all elastic and inelastic processes. Inelastic channels
include the vibrational modes r
v1
(the bending mode with threshold 0.198 eV), r
v2
(the sum of two
stretching modes with thresholds 0.453 and 0.466 eV), and r
v3
(a lump sum of other vibrational
excitation modes including higher hormonics and combinational modes with an assigned threshold
of 1 eV). The electronic excitations r
e1
and r
e2
have threshold energies of 7.5 and 13.3 eV. Ionization
cross sections are those of Djuric et al. (o), and Bolarizadah and Rudd (.). (From Ref. 19.)
Report 55 [36]. Because of experimental constraints, most dierential cross-section
measurements are undertaken in electron beam experiments with the energy spectra of
ejected electrons being measured at various emission angles. This type of measurement
results in the determination of doubly (single-electron spectrometer) or triply (two-
electron spectrometers in coincidence) dierential cross sections. Although the triple
dierential cross sections, which provide a complete kinematic description of the collision,
have been the subject of much study in physics (for a review, see Ref. 37), the major studies
of radiological and radiochemical importance for ionization by fast electrons have been
conned primarily to doubly dierential cross sections (see Sec. 4.4.2 for the use of these
cross sections for track simulation). The measured quantity is generally presented as r(e
p
,
e
s
, h
s
), or simply r(e
s
, h
s
), where e
p
is the energy of the incident or primary electron, e
s
is
the energy of the secondary or ejected electron, and h
s
is the emission angle of the
secondary electron relative to the direction of the incident primary electron. From doubly
dierential cross sections, one can readily obtain singly dierential cross sections r(e),
dierential in electron energy q, by integration with respect to the emission angle
re 2p
_
p
0
re; hsinh dh; 11
or single dierential cross sections r(h), dierential in emission angle, by integration over
ejected electron energy
rh 2p
_
e
max
0
re; hsinh de: 12
In the same manner, one can determine the total ionization cross sections r
T
by
integration of the doubly dierential cross sections over both ejected electron energy
and emission angle
r
T
2p
_
e
max
0
de
_
p
0
re; hsinh dh 13
Doubly dierential cross sections for ionization of water vapor by 1-keV electrons
from the work of Bolorizadeh and Rudd [38] are shown in Fig. 4. Here the spectrum of
electrons emitted with emission angles ranging from 10j to 150j are shown. Because
electrons are indistinguishable, the low-energy electrons, e<1/2 e
p
, are commonly des-
ignated as secondary electrons, and electrons with energies e>1/2 e
p
are considered the
primary electrons that have undergone inelastic collisions; the very narrow line prole of
the elastically scattered 1-keV electrons is not shown in Fig. 4. The spectra shown in Fig. 4
illustrate that the probability, as reected in the cross sections, of producing low-energy
secondary electrons is essentially independent of emission angle, whereas the probability
of scattering a primary electron to a large angle rapidly decreases with angle.
The angular distribution of ejected electrons of selected energies from ionization of
water vapor by 1-keV electrons is shown in Fig. 5. This illustration explicitly shows the
isotropic nature of the cross sections for ejection of electrons with low energies. These low-
energy secondary electron cross sections are representative of the angular distributions
resulting from distant, or soft, collisions. At an ejected energy of 100 eV, we begin to see a
peak forming at about 70j, and this peak moves to smaller angles for secondary
electron energies of 350 and 500 eV. The relatively broad peaks kinematically correspond
to close collisions between the incident primary and target electrons.
Kim and Rudd [39] have provided an excellent review of the theoretical techniques
used to describe ionization of atoms and molecules by fast electrons and that have been
Figure 4 Doubly dierential cross sections for the ionization of water vapor by 1-keV electron
impact. (From Ref. 38.)
Figure 5 Angular distributions for selected energies of electrons ejected from water vapor by 1-
keV electron impact. (From Ref. 38.)
used to develop models for determining the dierential ionization cross sections used in
numerous applications. The interaction of an electron with a free electron was rst
investigated by Rutherford as a simple coulomb interaction between two charged particles.
The Rutherford equation, dierential in energy loss W, was given as
drW; T
dW

4pa
2
o
Z
2
1
R
2
T
1
W
2
; 14
where W is the energy of the ejected electron, Z
I
is the atomic number of the incident
charged particle (Z
I
=1 for incident fast electrons), R is the Rydberg unit of energy (13.6
eV), a
o
is the classical Bohr radius (0.0529 nm), and T is the incident particles scaled
kinetic energy (T=1/2 m
e
v
2
, where v is the particle velocity and m
e
is the electron mass).
However, the Rutherford formula fails for electron impact because it does not account for
electron exchange, a process brought about because of the indistinguishability of the two
colliding electrons. The Mott formula is a generalization of the Rutherford equation that
includes electron exchange. The Mott cross section for an electron collision with a free
electron is given by
drW; T
dW

4pa
2
o
R
2
T
1
W
2

1
WT W

1
T W
2
_ _
; 15
where the rst term in the brackets corresponds to the Rutherford direct collision term,
the second term results from interference between the direct and exchange collision terms,
and the last term represents the exchange collision term. We should emphasize that the
Mott cross section still applies to a collision with a free electron. To account for the fact
that the electron is bound with energy B in an atom or molecule, one can introduce the
binding energy through E = W+B and rewrite the Rutherford formula, Eq. (14), with a
simple replacement of E for W. The corresponding Mott formula of Eq. (15) can be
rewritten as
drW; T
dW

4pa
2
o
R
2
N
T
1
E
2

1
ET W

1
T W
2
_ _
; 16
where N is now the number of electrons with binding energy B. However, this replacement
to account for a binding energy comes at a cost because both the modied Rutherford and
Mott formulas are good approximations only for energy loss E much larger than the
binding energy B.
These classical formulas still do not account for the motion of the bound electrons in
the atom or molecule. To be more appropriate to the interaction of an incident electron
with the bound target electron, one must recognize that the velocity vector of the bound
electron can be randomly oriented with respect to the incident electron providing a
broadening of the energy of the secondary electron as calculated by the modied Mott
cross section. If one integrates over the velocity distribution of the bound electron, the
more familiar binary encounter approximation is derived that, in its simplest form, is given
by Kim and Rudd [39] as
drE; T
dE

4pa
2
o
R
2
N
T U B
1
E
2

1
ET W

1
T W
2
_ _
4U
3
1
E
3

1
T W
3
_ _ 17
where U is the average kinetic energy of an electron with binding energy B given by U
h p
!
2
i=2m and p
!
is the momentum operator for the electrons in the subshell under con-
sideration.
Although these semiclassical approaches to electron impact ionization tend to be
reasonably accurate at predicting the cross sections for large momentum transfer, when
integrated with respect to energy loss, the total ionization cross section derived suers
from having an incorrect asymptotic high-energy dependence on the incident electron
energy. The energy dependence of the total cross section varies as T
1
, whereas
experimental evidence, and more complete quantum mechanical descriptions of the energy
loss process, suggests that the asymptotic dependence should be T
1
lnT.
The rst quantum mechanical approach to describe the interaction of charged
particles with atomic systems was that of Bohr, who considered the interaction in terms
of an impulse approximation resulting in the transfer of energy and momentum from the
incident charged particle to the atom or molecule. This perturbation approach was further
developed by Bethe in the 1930s; an extensive review of this work has been published by
Inokuti [40]. The Bethe theory provides the basis for a quantum mechanical understanding
of collisions of fast charged particles with atomic and molecular targets. Within the Bethe
theory, the dierential cross section for energy loss can be expressed [41] as
dr
dW

4pa
2
o
Z
2
T
N
k1
R
2
E
k
df
k
dW
ln
4RT
E
2
k
_ _
b
k
W O
E
k
T
_ _
; 18
where df
k
/dW is the partial optical oscillator strength for ejection of an electron with
energy W by photoionization of the kth subshell of the target, and E
k
is the total energy
transfer given by W+B
k
. Expressed in this way, the rst term in Eq. (18) represents the
contributions to the cross sections from soft collisions, the second term represents the hard
collisions contributions, and the last term includes contributions of higher order in powers
of T
1
. The optical nature of soft collisions is clearly illustrated by the relationship to
optical oscillator strengths. As expressed in Eq. (18), the contributions from exchange to
electron impact excitation and ionization are not included. A more complete description of
the use of the Bethe theory for the study of energy loss by electrons, including electron
exchange, is given by Dingfelder et al. [42].
The strength of the Bethe approximation is that it properly treats soft collisions,
thereby giving the proper energy dependence T
1
lnT for the total ionization cross
sections. A weakness of the Bethe approximation is the computational diculty,
including the need for accurate wave functions for all initial bound and nal continuum
states. Still it can be a powerful tool for the calculation of cross sections representative of
the target structure through the use of appropriate measured target oscillator strengths
to evaluate matrix elements otherwise dicult to obtain (see Ref. 42 and references
therein).
By careful inspection of the relationships of the semiclassical close collision
approximations and Bethe formula, one can obtain simple and accurate information on
ionization cross sections. By the method rst proposed by Platzman, and used extensively
by others, it is instructive to form the ratio of the dierential cross sections [measured
r(W,T) or calculated dr(W,T)/dW)] to the Rutherford cross section. This ratio, called Y,
is mathematically dened as
Y
drW; T
dW
T
4pa
2
o
E
2
R
2
19
and has the property that if plotted as a function of R/E, the integral is proportional to the
total ionization cross section
_
YT; WdR=E r
ion
T
T
4pa
2
o
R
:
20
Therefore when experimental data are plotted as Y vs. R/E, the relative importance of
electrons of dierent energies as contributors to the total ionization cross section is clearly
apparent and the relative magnitude of the dierential cross sections must be such that the
area under the curve is equal to the total ionization cross section [43]. The latter point is
particularly important because total ionization cross sections can generally be obtained
more accurately than dierential cross sections. Because Eq. (20) is a sum over energy loss
to all electrons, in the limit of large secondary energy the ratio Y tends to a value equal
to the number of electrons in the target. If dr(W,T)/dW given by the Bethe formula of
Eq. (18) is inserted in Eq. (19) and terms in higher-order T are considered negligible, one
can focus on the low-energy electrons, soft collisions, dominated by the rst term in the
Bethe theory
Yi
N
k1
E
k
df
k
dW
ln
4RT
E
2
k
_ _
: 21
If we now plot Y as a function of R/E, owing to the small variation of the logarithm term
with low-energy ejected electron energy, the ratio Y is expected to have the same general
structure with ejected electron energy as
N
k1
E
k
df
k
dW
, i.e., as the optical oscillator strength
multiplied by the energy loss.
An example of the utility of the Platzman Plot from the work of Kim [44] is shown
in Fig. 6 where single dierential cross sections for ionization of N
2
by electrons are
shown. Here the low-energy ejected electron spectra have the characteristic shape of the
optical oscillator strengths multiplied by the energy loss, Edf/dW, and the magnitude of
the cross sections are determined such that the areas under the curves are proportional to
the total ionization cross section. At the lowest incident electron energies, the optical
nature of the spectra tends to disappear as close, nondipole, interactions dominate. Note
also that as the ejected electron energy increases, the Rutherford ratio approaches a value
equal to the number of active, outer shell, electrons in the molecule. This type of plot
provides an excellent means to evaluate the internal consistency and accuracy of
experimental cross sections. The cross sections for ionization of water vapor by electron
impact measured by Bolorizadeh and Rudd [38] are shown in Fig. 7 along with the
distribution obtained from the dipole oscillator strengths [45]. Note that the low-energy
electrons do not decrease as would be expected by the shape of Edf/dW, indicating that
some extra electrons are probably being detected from scattering events in the exper-
imental system. However, the high-energy electrons ejected from fast collisions do
approach a value near 10, in agreement with the number of electrons in the water
molecule. Note that the very rapid rise in the ratio at the extreme high energy end of
each spectra is an eect of the indistinguishability of electrons and results from the elastic
scattering contribution to the spectrum.
Because the semiclassical theories can be used to calculate dierential cross sections
with relative ease for close collisions between the incident charged particle and the bound
electron, and the Bethe theory provides a straightforward method to describe low-energy
electrons ejected in distant collisions, it is only natural to combine the best characteristics
of the two approaches to derive a comprehensive description of electron impact ionization.
Figure 6 A Platzman plot of the ratio of the secondary electron cross sections for ionization of
N
2
by electrons to the comparable Rutherford cross sections. Q is the energy loss, Q = W+B, and is
equivalent to the parameter E used in the text. (From Ref. 44.)
Figure 7 The ratio of measured single dierential secondary electron production cross sections to
the corresponding Rutherfordcross sections for ionizationof water vapor by electrons. (FromRef. 38.)
Kim and Rudd [39] have developed such a model, the binary encounter dipole (BED)
model, in which the dierential ionization cross sections are given by
drW; T
dW

4pa
2
o
N
Bt u 1
R
B
_ _
2
N
i
=N 2
t 1
1
w 1

1
t w
_ _ _
22
2 N
i
=N
1
w 1
2

1
t w
2
_ _
lnt
Nw 1
dfw
dw
_
where t = T/B, w = W/B, u = U/B, N is the number of electrons in the subshell, df/dW
is the dierential dipole oscillator strength of the electron in this subshell with binding
energy B, and N
i
is obtained from the dierential oscillator strength distribution by
N
i

_
l
0
df w
dW
dW: 23
This relationship becomes very useful because dipole oscillator strengths are available for
a wide selection of atoms and molecules. The authors also provide a means of modifying
this equation for use when oscillator strengths are not available; the interested reader is
directed to their work [39] for additional details. The strength of their work is also evident
in that it provides a functional relationship for the determination of total cross section as
well. By integration of the single dierential cross sections, one obtains
r
i

4pa
2
o
N
t u 1
R
B
_ _
2
Dtlnt 2
N
i
N
_ _
t 1
t
_ _
lnt
t 1
_ _ _ _
; 24
where
Dt N
1
_
t1=2
0
1
w 1
dfw
dw
dw: 25
Both the single dierential and total ionization cross sections derived from these
models have been very successful in reproducing reliable experimental results. Because of
the dominance of the dipole term for low-energy ejected electron energies, one would
expect that the normal dipole distribution, as a function of angle for these electrons and
the high-energy electrons, will have an angular distribution described by the kinematic
constraints of the binary encounter theory.
5.2. Ionization by Protons and Other Bare Ions
As with the study of cross sections for electron impact discussed above, the decades of the
1970s and 1980s saw rapid advances in our understanding of ionization by fast protons
and other heavy charged particles; see, e.g., reviews presented in Refs. 10, 36, and 46.
Experimental studies have focused on the measurement of doubly dierential cross
sections, dierential in ejected electron energy and emission angle, for protons with
energies from a few tens of keV to several MeV. Measurements have also been conducted
for He
+
and He
2+
impact; however, these data are not nearly as comprehensive, and a few
measurements were made for ions of C, O, Ne, and Ar. As with electron impact,
measurements of electron emission cross sections are conducted for atoms and molecules
in gas phase owing to the very short range of low-energy electrons and residual ions in
condensed phase material.
The process of ionization by protons, and other bare ions, is essentially the same as
that described above for incident electrons, except that heavy ions and their secondary
electron are distinguishable, removing the need to consider exchange processes, and these
projectiles, being much heavier than the secondary electrons, will travel predominantly in
a straight line. One also must be more careful in describing ionization for heavy charged
particles because ionization of the target atom or molecule can occur with either the
release of a free electron, as with electron impact, or by the charged particle capturing an
electron from the target. In the latter case, a residual ion is produced, but no free electron
is released; thus one needs to specify whether ionization measurements are measuring free
electrons or residual ionsfor ionization by heavy ions, these cross sections are dierent.
As with electron impact, one can see a division of energy loss events occurring
between either from soft or hard collisions. The spectra of electrons ejected from H
2
and
N
2
at 20j with respect to an incident 1-MeV proton is shown in Fig. 8; these data are from
the work of Toburen et al., Refs. 47 and 48, respectively. Note the rather clear separation
between the low-energy peak in the cross sections at near zero ejected electron energy and
the high-energy peak near 3000 eV; the high-energy peak is the so-called binary encounter
peak. The electron energy W and emission angle h observed for the high-energy peak are
related to the kinematics of the system as
W
4MmE
p
M m
2
cos
2
h; 26
where M is the incident ion mass, m is the electron mass, and E
p
is the incident ion energy
in MeV/u. The shape and width of the binary encounter peak is determined by the velocity
distribution of the initially bound electron, i.e., the Compton prole. The largest dier-
ences between the two spectra shown in Fig. 8, other than the N
2
cross sections being
Figure 8 Electron emission at 20j with respect to the forward direction of the proton for ion-
ization of H
2
and N
2
by fast proton impact. The data for ionization of H
2
are from Ref. 47 and those
for N
2
are from Ref. 48.
about an order of magnitude larger, are the contributions to the spectra at about 360 eV
from Auger electrons emitted following inner-shell ionization of the nitrogen atom, and
the larger contribution of electrons in the energy region from about 200 to 1500 eV in the
N
2
spectrum relative to the H
2
spectrum. Cross sections in this intermediate-energy region
are somewhat enhanced by contributions from electrons ejected from inner shells of the
nitrogen molecule, in contrast to the spectrum from hydrogen where only a single shell is
involved. Because the experiments generally do not determine the initial state of the ejected
electron, these spectra are an average over all initial bound states.
An example of the extent of the data obtained in typical measurements of doubly
dierential cross sections is shown in Fig. 9 for ionization of CH
4
by 1-MeV protons. This
example from the work of Lynch et al. [49] also serves to illustrate the features of the
spectra of electrons ejected from molecules by fast protons. This three-dimensional display
shows the isotropic nature of the ejection of low-energy electrons and the sharply dened
angular dependence of the binary encounter peaks in the ejection of high-energy electrons.
The ridge formed by the binary encounter electrons across the dierent angles is
commonly referred to as the Bethe ridge [40] and the peak energies are approximately
given by the expression provided by Eq. (26). One can also see a ridge running across the
surface for electron energies of approximately 250 eV. This ridge results from Auger
electron emission following ionization of the K shell of carbon in the CH
4
molecule. For
Figure 9 Energy and angular distribution of cross sections for electron emission from CH
4
following 1.0-MeV proton impact. (From Ref. 49.)
low atomic number elements, such as carbon, the uorescence yield is very small (x
K
c
0.0024 for carbon), meaning that the cross sections for Auger electron emission are
essentially identical to the cross sections for K-shell ionization. Thus secondary electron
spectra, such as these shown in Fig. 9, provide a good source of information on inner-shell
ionization cross sections.
The theoretical descriptions of the ejected electron spectra for heavy ion impact are
basically the same as that for electron impact discussed above, except that the theory is
simplied for heavy ions because exchange forces are not an issue. One can write the
equivalent of Eq. (17) for the binary encounter approximation to the single dierential
ionization cross sections for bare heavy ion impact [36] as
drE; T
dE

4pa
2
o
Z
2
1
R
2
TE
2
1
4U
3E
_ _
27
for E
z E z 0, and
drE; T
dE

4pa
2
o
Z
2
1
R
2
TE
2
U
E
4
3
T
U
_ _
3=2
1
6
E
U
1
_ _
1=2
1
_ _ _ _
3
28
for E
+
z E z E
, where E
F
= 4T F4(TU)
1/2
, Z
I
is the charge of the incident ion, and the
other parameters were dened above for Eq. (17). For heavy ions, as dened above for
electrons, the kinetic energy T of the incident ion is given as T = m
e
v
2
p
/2, where m
e
is the
electron mass and v
p
is the incident particle velocity; thus T is the energy of the incident
particle in terms of the equivalent velocity electron. The agreement between experiment
and results of binary encounter theory can be somewhat improved by integrating over a
Fock distribution of orbital electron velocities, rather than a simple hydrogenic distribu-
tion, as was shown by Rudd et al. [50]; however, for light atoms, the hydrogenic
distribution is also a good approximation.
More detailed information on the characteristics of secondary electron emission can
be obtained by consideration of the angular distributions of the double dierential cross
sections for electron production by fast ions. A comparison of the results of the binary
encounter approximation, the quantum mechanical Born approximation, and experimen-
tal results is shown in Fig. 10 for ionization of helium by 2-MeV protons. These cross
sections clearly illustrate the isotropic nature of low-energy electron emission compared
with the sharply peaked angular distributions for high-energy electrons. The theoretical
results shown in Fig. 10 include a plane wave Born approximation (PWBA) of Madison
[51] in which the author used HartreeFock initial discrete and nal continuum wave
functions, and the binary encounter approximation (BEA) of Bonsen and Vriens [52] in
which they average over the initial velocity distribution of the bound electrons. Notice that
the BEA is more sharply peaked in angle than the quantum mechanical result. It should be
noted that the PWBA results using hydrogenic wave functions provides essentially the
same results as the BEA. Although the PWBA calculations of Madison are in much better
agreement with experimental data than the BEA, there are still discrepancies for small
angles and ejected electron velocities less than and near that of the proton velocity, i.e.,
equivalent to electron energies less than or equal to E
e
= m
e
v
p
2
/2. For the particle energy
shown in Fig. 10, this occurs at electron energies of approximately 1 keV and less. This
enhancement of the cross sections for small angles of emission has been attributed to an
ionization mechanism called charge transfer to continuum states of the proton, an
additional ionization channel not included in the PWBA calculation [53].
Figure 10 Angular distributions of electrons ejected from helium by 2-MeV protons. The
experimental data are from Ref. 54; theoretical results are the binary encounter approximation of
Bonsen and Vriens [52]; and the plan wave is the Born calculation of Madison [51].
As was discussed for electron impact, the classical Rutherford formula, Eq. (14), and
Bethe theory, Eq. (18), provide excellent tests of the asymptotic features of the singly
dierential cross sections for electron emission in fast proton, or other bare ions, in
collisions with atoms and molecules. The Platzman plot, a plot of the ratio of measured
single dierential cross sections to the Rutherford cross section as a function of the R/E, is
shown in Fig. 11 for ionization of helium by protons [54]. Note that from small values of
R/E (energetic ejected electrons), the ratio tends to a value of 2 as expected from the
number of electrons in the atom, and the spectra of low-energy ejected electrons has the
general shape expected from Edf/dW as predicted by the Bethe theory. The use of the Ru-
therford ratio was also proposed by Kim [55] as an excellent method to test the absolute
accuracy of ionization cross sections by plotting the Rutherford ratio as a function of E/R,
in which case the ratio should reach a asymptotic value for ejection of high-energy
electrons equal to the number of electrons in the atom. This use of the quantity Y is shown
in Fig. 12 for ionization of helium by protons. The dashed line in Fig. 12 is the predicted
ratio for emission of high-energy electrons. The experimental results presented by Manson
et al. [54] are measured absolute cross sections, and they are in excellent agreement with the
expected cross sections based on the Rutherford theory. There is some evidence from this
ratio that the experimental results might actually be as much as 10% larger than expected
from Rutherford theorythis dierence is well within the stated 25% uncertainties of the
absolute values of the experimental data, suggesting that a renormalization to the
asymptotic Rutherford value might be advised. From the data shown in Fig. 12, we see
that, for the asymptotic form of the ratio Y to be reached requires incident proton energies
greater than about 500 keV. At lower energies, the Rutherford plateau is not reached by
the most energetic of the ejected electrons.
Doubly dierential cross sections for electron emission following proton impact have
been measured for a wide variety of dierent atomic and molecular target systems (for
Figure 11 A Platzman plot, the ratio of the experimental single dierential cross section for
electron emission from helium by 1-MeV protons to the corresponding Rutherford cross sections
plotted as a function of R/E. The experimental cross sections are from Ref. 54 and the dierential
oscillator strength is taken from Ref. 43.
details, see reviews of these data in Refs. 10, 36, 46, and 56) providing an opportunity to
explore the eects of target and projectile parameters on the interaction cross sections. For
molecules composed of second-row elements, where only K and L shells are involved, the
cross sections for ejection of fast electrons is observed to be approximately proportional to
the number of electrons in the atom or molecule. This is illustrated in Fig. 13 where the
single dierential cross sections for ionization of a number of molecules are plotted per
eective target electron for ionization by 1-MeV protons; hydrocarbon data are from
Refs. 49 and 57 and the oxygen-containing molecular data are from Ref. 58. The number
of eective electrons used here is simply the number of outer-shell electrons, and this is
determined by subtracting the number of K-shell electrons from the total number of
electrons in the molecule. Note that the dierences in the spectra scaled in this manner
occur only in the regions of Auger electron emission and for electron energies less than
about 50 eV. The Auger electron peak energies depend on the K-shell binding energies and
occur at about 250 eV for carbon, 365 eV for nitrogen, and 540 eV for oxygen; for the
energy resolution used in these measurements, about 4%, the ne structural details of the
spectra are not observed [59]. The dierences in the spectra for low-energy electron
emission reect the dierences in oscillator strength distributions for the dierent
molecules as is expected from the Bethe theory.
It is also interesting to examine the angular distributions of these doubly dierential
cross sections for low-Z molecules. Angular distributions of cross sections scaled by the
number of outer-shell electrons for selected energies of electrons ejected by 1-MeV protons
are shown in Fig. 14. Scaled in this manner, cross sections for these molecules are in
excellent agreement with one another except for those of molecular hydrogen. The
hydrogen cross sections are much more sharply peaked in emission angle, and in this
Figure 12 The ratio of the measured single dierential cross section for ionization of helium by
protons to the corresponding Rutherford cross sections plotted as a function of the ejected electron
energy. The solid line represents the expected high-energy behavior of the ratio; it should approach
the number of electrons in the atom. The measurements are from Manson et al. [54].
way reect the results of theoretical calculations that employ hydrogenic wave functions,
as was also observed in the data shown in Fig. 10.
The relative success of the binary encounter and Bethe theories, and the relatively
well established systematic trends observed in the measured dierential cross sections
for ionization by fast protons, has stimulated the development of models that can extend
the range of data for use in various applications. It is clear that the low-energy portion of
the secondary electron spectra are related to the optical oscillator strength and that the
ejection of fast electrons can be predicted reasonable well by the binary encounter theory.
The question is how to merge these two concepts to predict the full spectrum.
Miller et al. [60,61] examined the structure of the BetheBorn formula and observed
that the second term of Eq. (18), the hard collisions term, is independent of the projectile
properties. In addition, for many target atoms and molecules, the optical oscillator
strength has been measured, making evaluation of the rst term readily accessible. Thus
if the higher-order terms in E/T can be ignored and experimental data are available for
single dierential cross sections, even for a very limited incident ion energy range, it should
be possible to extract the hard collisions term from the experimental data. Because the
hard collision contribution is independent of particle energy, it can be used along with the
rst term in the Bethe formula to obtain dierential cross sections throughout the range of
validity of the Bethe formula. This model was shown to be very useful in predicting the
Figure 13 Singly dierential cross sections for ionization of several molecular targets by 1-MeV
protons are plotted as a function of the ejected electron energy. The cross sections are scaled by the
eective number of target electrons in each molecule; the eective number of electrons is dened as
the total number of molecular electrons minus those of the K-shell. (From Refs. 49, 56, and 58.)
single dierential cross sections where limited data existed, and in improving the accuracy
of low-energy electron cross sections where experimental artifacts can render measure-
ments unreliable. Their model uses the optical oscillator strengths to determine the shape
of low-energy electron cross sections where experimental accuracy can be lacking.
However, the model was limited to fast protons by the high-energy nature of the theory.
The most comprehensive model of secondary electron emission by bare charged
particles has been developed by Rudd [62] for secondary electron production by protons;
Figure 14 Doubly dierential cross sections for ionization of several low-Z molecular targets by 1-
MeV protons plotted for selected ejected electron energies as a function of the emission angle. (From
Refs. 47, 48, 5658.)
this model is described in detail in ICRU Report 55 [36] and in an excellent review by
Rudd et al. [63]. Rudds model has the advantage of being applicable to the full range of
incident proton and ejected electron energies. It has the proper asymptotic dependence on
proton energy at both low and high energies. The major shortcoming is that it must be t
to sucient experimental data to x the models 10 parameters. For those target atoms
and molecules where parameters have been xed, it is a powerful tool because of its
analytic capabilities for application in elds such as radiation chemistry and biology that
need secondary electron spectra to evaluate subsequent chemical reactivity. Rudds
formula is given as
drW; T
dW

S=BF
1
F
2
W1 W
3
1 expaW W
c
=v
; 29
where S=4pa
o
2
N(R/B)
2
and W
c
is the cuto energy given by
W
c
4v
2
2v R=4B; 30
N is the number of electrons initially bound with energy B, v is the ion velocity, and W is
the ejected electron energy. The functions F
1
and F
2
are given as
F
1
v L
1
H
1
31
and
F
2
v L
2
H
2
=L
2
H
2
; 32
with
H
1
A
1
ln1 v
2
=v
2
B
1
=v
2
; 33
L
1
C
1
v
D
1
=1 E
1
v
D
1
4
; 34
H
2
A
2
=v
2
B
2
=v
4
; 35
and
L
2
C
2
v
D
2
: 36
The 10 parameters A
1
, B
1
, C
1
, D
1
, E
1
, A
2
, B
2
, C
2
, D
2
, and a are given in both Refs. 36 and
63 for 10 dierent atomic and molecular targets. An indication of the accuracy of the
cross section provided by the Rudd model is illustrated in Fig. 15, where cross sections for
ionization of N
2
by protons is compared to measurements [48,6466] over a wide energy
range. The major advantage of this model is that it is accurate for both low-energy and
high-energy protons where most models have been developed for only high-energy
ions.
5.3. Ionization by Dressed Ions
Perhaps the greatest challenge for the detailed investigation of energy deposition by heavy
charged particles occurs at particle velocities where the capture of electrons become
probable and cross sections must be determined for the interaction of dressed ions with
target electrons. As an ion captures electrons, these electrons can partially shield the ion
nucleus from coulomb interactions with the electrons of the medium. For example, a
proton with a bound electron (a moving hydrogen atom) looks like a neutral particle from
a large distance and might be expected to have little probability of interacting with
electrons of the target medium. However, this is far from what is actually observed; the
moving hydrogen atom can actually be as eective as a proton in producing ionization of
the target. To explain this phenomenon, we recall that the hydrogen electron in its ground
state is bound with a spherically symmetric probability distribution having its maximum at
the Bohn radius. As we approach the hydrogen atom on a microscopic scale, this charge
distribution provides somewhat less than a full charge screening of the nucleusthe unit
of electronic charge is distributed over the orbital volume of the ground state of the atom.
In fact, if we were inside the Bohr radius, we would expect little or no screening of the
nucleus by the bound electron. This distance-dependent shielding of the nucleus by bound
electrons occurs for all dressed particles and results in ejection of low-energy ionization
electrons, those produced in large impact parameter (soft) collisions, with a reduced
probability owing to a more eective screening of the projectile charge at large distances.
On the other hand, the ejection of high-energy electrons, those produced in small impact
parameter (hard) collisions, will show little eect of screening by the projectile electron(s)
because the impact parameter can be inside of some, or all, of the distributions of bound
electrons. In addition, the electrons bound to the moving particle must be considered as
active participants in the collision. They can also interact with target electrons via their
coulomb charge and can either be ionized in the collision leading to free electrons in the
media frame of reference with velocity comparable to the projectile (elastic scattering), or
they can interact with the bound electrons of the media producing excitation or ionization
(inelastic scattering) of the target. The interactions of projectile electrons with target
Figure 15 The ratio of calculated and measured single dierential cross sections for electron
emission from N
2
following proton impact to the corresponding Rutherford cross sections. The solid
line is the result of the model of Rudd [62]; experimental data are from Rudd (o) [64], Crooks and
Rudd (.) [65], Toburen () [48], and Stolterfoht (5) [66].
electrons is complicated by the convolution of the initial velocity distributions resulting
from their binding, with the velocity of the moving projectile, and conversion of these
vectors to the medium (laboratory) frame-of-reference.
An example of the features of the spectrum of secondary electrons emitted in H
o
impact on water molecules from the work of Bolorizadeh and Rudd [67] is shown in Fig.
16. Compared to the simple spectrum of electrons emitted by proton impact shown as the
solid line in Fig. 16 the spectrum from H
o
impact has an additional peak centered at an
electron energy of approximately 82 eV. This broad peak is from the superposition of the
spectrum of electrons stripped (elastically scattered) from the projectile on the spectrum of
electrons ejected from the target. Because the stripped projectile electrons originate as
bound electrons in the rest frame of the moving projectile, their laboratory energy is given
approximately by W = m
e
E
p
/M
p
and the width of the peak is determined by the Compton
prole of electrons in the projectile frame, but also transformed to the laboratory frame-
of-reference. The results shown in Fig. 16 clearly illustrate that the cross-sections for
Figure 16 Ionization of water vapor by 150-keV H
o
particles. The e
and H
o
impact data are from
Refs. 38 and 67, and the parameters for the Rudd model are from Ref. 36. The dotted line is
discussed in the text under the section on eective charge.
electron production by fast neutral hydrogen atoms can actually be larger than those
for the comparable velocity proton. Owing to screening by the projectile electron, we
might expect low-energy electrons emitted from the target in soft collision to be suppressed
relative to the bare proton (as predicted by the dashed line in Fig. 16). However, for
ionization by H
o
, this eect of screening is compensated by contributions from elastic
scattering of projectile electrons (the electron loss peak at 82 eV in this case) and by the
very low-energy electrons produced by inelastic scattering of projectile electrons from
target electrons resulting in ionization of the target. The dashed lines in Fig. 16 are from
the cross sections for inelastic energy loss by electrons with energies representative of those
in the elastic peak, the data come from the work of Bolorizadeh and Rudd [38]. To predict
the full extent of the low-energy inelastic scattering contribution to the spectra requires
integration of the inelastic cross sections over the weighted distribution of projectile
electron velocities.
For more complex projectiles and targets, additional features become apparent in
the spectra of ejected electrons. Doubly dierential cross sections for ionization of CH
4
by
0.3 MeV/u C
+
ions (3.6 MeV total projectile energy), taken from some of the authors
unpublished work, are shown in Fig. 17 to illustrate the increasing complexity of dressed-
ion collisions compared to that for bare ions represented in Fig. 9 by proton impact. In
Fig. 17, the cross sections are seen to have their maximum at very low energy ejected
electrons as was the case for proton impact, and, although their shape is not as sharp and
Figure 17 Ionization of CH
4
by 0.3-MeV/u C
+
ions. (These are unpublished data of Toburen
discussed in Ref. 56.)
discrete for this intermediate velocity ion as for the higher velocity proton impact, there is
a broad distribution of binary encounter electrons at the kinematically predicted forward
angles. In addition, we see evidence of K-Auger emission following the inner-shell
ionization of the target carbon atom as a ridge in the surface at approximately 250 eV;
this is most clearly seen for large angles. At small angles, the Auger electron yield becomes
insignicant relative to electrons directly ejected from outer shells. The broad peak at
about 160 eV, most strongly seen for small angles, results from electrons stripped from the
projectile, and Auger electrons resulting from excitation of the K-shell of the projectile are
observed as the Doppler-shifted Auger peaks superimposed on the continuum spectrum at
the high-energy edge of the binary encounter peaks. Although electrons stripped from the
projectile are predominantly observed ejected into small angles, there is also evidence of
their presence in the spectra at large angles.
Most of the features of the secondary electron spectra induced by impact of dressed
ions can be simply explained by the combined eects of the individual interactions of the
incident ion and its bound electrons with the target. However, a quantitative description is
complicated by the eects of electron binding and nuclear screening by bound electrons.
As discussed above for the calculation of stopping power for dressed ions, the eects of
bound projectile electrons on target ionization can be included through use of an eective
projectile charge. However, it is clear that a useful eective charge must be a function of
energy loss to be able to adequately describe the eects of electron screening on the
secondary electron emission spectra induced by dressed ions. To simply multiply the
spectrum of electrons induced by bare ions by a constant factor, such as the eective
charge determined from stopping power, would not provide a realistic estimation of the
spectra of electrons ejected in collisions involving dressed ions. This will be explored in
detail in the next section of this chapter.
6. EFFECTIVE CHARGE
As we have seen, the spectra of electrons ejected from a target atom or molecule by dressed
ions and neutrals are quite dierent from those induced by bare projectiles. These
dierences cannot be explained by use of a simple eective charge as was dened by
stropping power theory. For fast relatively simple dressed ions, such as H
o
or He
+
, the
separation of target and projectile ionization is relatively straightforward. The single
dierential cross sections for ionization of water vapor by 2-MeV He
+
and He
2+
ions
from the work of Toburen and Wilson [68] are shown in Fig. 18. For comparison, the data
for He
2+
ion impact has been scaled by z
2
(divided by 4) to represent the spectrum
expected of a bare singly charged ion (e.g., similar to proton impact at the same velocity as
the He
+
ion); this is shown as the solid line. The cross sections for He
+
impact are in good
agreement with the singly charged ion impact for electrons ejected with low energies (soft,
or distant, collisions), whereas the high-energy ejected electron cross sections are in
excellent agreement with the He
2+
results showing that screening is inecient in these
close collisions. The dashed line in Fig. 18 is simply a free-hand interpolation of target
ionization in the energy region containing the peak from electrons stripped from the
projectile. From experimental data such as these, one can determine the eective nuclear
charge as a function of energy loss from the formula
z
eff
E z
drE; q
dE
_
drE; z
dE
_ _
1=2
; 37
where dr(E,q)/dE is the measured dierential cross section for target ionization by an
incident ion of charge q and dr(E,z)/dE is the measured dierential cross section for
energy loss E by the bare ion of charge z. An example of z
e
(E) as a function of energy loss
obtained for ionization of He by He
+
ions is shown in Fig. 19. We must take care that the
portion of the electron spectrum that includes electrons from projectile stripping is not
included in the ratio, or that the stripping contribution is not included because they can
otherwise dominate the ratio. One can estimate the target ionization as was performed in
the case of the interpolated target contribution shown as the dashed line in Fig 18, or
simply use the portion of the electron spectra beyond the energy limitations of the stripped
projectile electrons. The origins of the theoretical curves shown in Fig. 19 will be discussed
in some detail below.
The theoretical basis for an eective charge z
e
(E) associated with collisional energy
loss has been investigated by several authors (see, e.g., Refs. 6972). Within the Born
approximation, the doubly dierential cross section for ejection of an electron with energy
W by a He
+
ion can be written as
A
2
r
AWAX

_
K
max
K
min
2
1
1 Ka
o
=4
2
2
_ _
2
IKdK; 38
where K is the momentum transfer, a
o
is the Bohr radius, and I(K) is a complicated
function of radial matrix elements and phase shifts [70]. The second term in the brackets
accounts for the eective screening of the nuclear charge by the bound helium electron.
Manson and Toburen have evaluated this expression using HartreeSlater wave functions
for initial discrete and nal continuum states for ionization of He by He
+
ions. Notice
that, within the Born approximation, the screening is a function of momentum transfer
and not energy transfer. The eect on energy transfer is obtained by an appropriate
Figure 18 Ionization of water vapor by 2-MeV He
+
and He
2+
ions. The dashed line is an estimate
of the contribution of target ionization by He
+
obtained by interpolation from regions beyond the
vicinity of electrons contributed by electron loss by the He
+
ion. (From Ref. 68.)
Figure 19 The upper portion of the gure shows the eective charge of the He
+
projectile as a
function of the ejected electron energy that is obtained from the experiment [68], Born theory [70],
and the model of Toburen et al. [71]. The lower portion of the gure is the same data, but plotted in
terms of the impact parameter. The impact parameter is obtained using the relationship between
projectile velocity, energy loss, and impact parameter dened by the Massey criterion. (See the text
and Ref. 71 for details.)
integral over momentum transfer. However, the eective charge for target ionization
calculated for electron emission at 60j using the Born approximation is in good agreement
with the measured single dierential cross sections shown in Fig. 19.
An important nding of the calculations using the Born approximation was that
there is a sizable contribution of target excitation (including ionization) that accompanies
projectile ionization. Doubly dierential cross sections for emission of 219 eV electrons
from He by 2 MeV He ions are shown in Fig. 20 with the results of PWBA calculations.
The peak in the distribution of electrons ejected at 0j in the laboratory frame of reference
is dominated by target ionization simultaneously occurring with projectile ionization. This
is in contrast to the binary encounter peak at about 70j that is attributed to target
ionization with projectiles left in the ground state, and to electrons ejected at large angles
(backward angles) where simultaneous excitation appears only of minor importance.
Figure 20 Doubly dierential cross sections for ejection of electrons of 219 eV (16 Ry) from He by
2-MeV He
+
ions. The points are measured cross sections and the calculated results are: line A
projectile ionization, target remains in the ground state; line Bprojectile ionization with
simultaneous target excitation; line Ctarget ionization, projectile remains in the ground state;
and line Dtarget ionization with simultaneous projectile excitation. (From Ref. 70.)
The evaluation of the I(K) term in Eq. (38) becomes increasingly dicult for more
complex target and projectile systems. This encouraged the development of a phenom-
enological approach for use with such systems. In the method proposed by Toburen et al.
[71], one considers the screening of the projectile by its bound electrons as a function of the
distance R from the nucleus as
z
eff
R z SR; 39
with
SR
i
N
i
_
R
0
w
i
r j j
2
r
2
dr; 40
where w
i
is the normalized radial wave function for the N
i
electrons residing in the ith
subshell of the projectile. To relate the energy loss E with the radial distance R, the Massy
adiabatic criterion R
ad
= v
p
/E is used, where v
p
is the incident ion or neutral particle
velocity and all parameters are in atomic units. Using this model, we obtain the solid line
in Fig. 19 in good agreement with both the experiment results and the Born calculation.
This model was also used to obtain the dotted line in Fig. 16 for target ionization of water
by atomic hydrogen impact. In the case of the neutral projectile, the model predicts zero
cross section for ionization involving zero-energy ejected electrons, i.e., for electrons
ejected by very distant collisions; this reects the lack of coulomb eld from the neutral
particle as observed at suciently large distances.
As noted above, the calculations including eects of screening by heavy ions and
interactions with complex targets, i.e., molecular targets, are dicult to accomplish by
fundamental theories such as is represented by the Born approximation. However, it is
possible to determine approximate cross sections by combining the model of Rudd,
described above for ionization by protons, with the screening model presented in Eqs. (39)
and (40). Single dierential cross sections for ionization of neon by protons and C
+
ions
of 0.1 MeV/u are shown in Fig. 21 along with these model predictions. The dotted line is
the result of Rudds model for ionization of neon by 0.1-MeV protons; it is in excellent
agreement with measured proton impact ionization cross sections for neon of Crooks and
Rudd [65] shown as the lled circles. A simple z
2
multiplication of the proton cross
sections, i.e., classical z
2
scaling, is shown by the solid line with lled points; notice the
large overestimation of the low-energy electron cross sections by this naive scaling
technique, although the high-energy portion of the spectrum is in relatively good agree-
ment with the measured cross sections. Applying the screening model for z
e
given by Eqs.
(39) and (40) above, evaluated using hydrogenic wave function for the electrons bound to
the carbon projectile, one obtains the solid line shown in Fig. 21. This application of the
screening model returns cross sections in much better agreement with the unpublished
measurement of Toburen throughout the energy range of the ejected electrons. There are
still dierences between measured and predicted cross sections in the intermediate electron
energy region, but the dierences have been reduced from factors of 30 or more at the
lowest ejected electron energies to a factor of about two at intermediate energies. The
remaining dierences might be due to overestimates of the amount of contribution from
continuum electron capture derived from scaling of the bare proton spectrum, or to simple
inaccuracies in the model.
From the discussion of projectile charge and its eect on the spectra of secondary
electron production, it is clear that the eective charge of the projectile is a function of the
ejected electron energy, i.e., projectile energy loss. From this it is evident that the single
value for eective charge obtained from stopping power theory cannot predict the dis-
tribution of secondary electrons that, through subsequent collisions in slowing, produce
the spatial patterns of energy deposition important to subsequent radiation chemistry.
7. CHARGE TRANSFER
As positively charged particles slow and reach velocities comparable to bound electron of
the medium, they capture and/or lose electrons. These processes can result in ionization of
the medium, with no free electron released (electron capture), or release of a free electron
from the projectile, with no concomitant target ion being produced (electron loss);
however, as pointed out above, these processes often occur with simultaneous ionization
of both the projectile and the target. The capture and lose of electrons by the projectile can
be an important energy loss mechanism for the incident particle (see Fig. 2) accounting for
as much as 1520% of the total energy-loss cross sections at their maximum. Although the
Figure 21 Cross sections form ionization of neon by 0.1-MeV/u protons and singly-charged
carbon ions. The experimental data for protons in from the work of Crooks and Rudd [65] and the
C
+
results are from some unpublished work of Toburen [56]. The results of Rudds model were
obtained using the parameters given in Ref. 36.
state-to-state electron transfer from target to projectile might not involve signicant
energy loss by the projectile (in some cases, an energy gain can be experienced), the kinetic
energy that must be gained by the captured electron to reach the velocity of the moving ion
can be signicant. For electron loss by a moving particle, the energy loss by the projectile
is simply the binding energy of the stripped electron, assuming energy is not contributed
by the velocity distribution of the target electrons that might aid in stripping the projectile
electron. With regard to the eects on subsequent chemistry, pure electron capture leaves a
residual ion, but no free electron and electron loss contributes a relatively energetic
electron to the track of the charged particle, with no residual target ion; again, in reality,
simultaneous excitation of the target or projectile often accompanies these processes.
Figure 22 Cross sections for electron capture by protons r
10
and electron loss by hydrogen atoms
r
01
for a number of molecular targets are shown scaled by the number of outer-shell target electrons.
(From Ref. 73.)
Because of the importance of electron capture and loss in a number of applied elds,
such as fusion plasma, atmospheric physics, and radiological physics, there has been
substantial eort contributed to the study of these events for simple collision systems, such
as protons and neutral hydrogen particles in simple gas targets. Less is known of the cross
sections for helium ions and neutrals, and only a few data exist for heavier ions (for a
recent review of the charge transfer data, see Ref. 73 and references therein). Data for
electron capture and loss cross sections for proton collisions with a few selected molecular
targets are shown in Fig. 22; these data are taken from the review of Toburen [73]. In this
example, the cross sections have been scaled by the number of target electrons using the
relatively naive assumption that the molecule simply provides a cluster of electrons
from which the moving ion can either capture or be ionized. Notice that this cross section
scaling is reasonably appropriate for fast collisions, i.e., ion energies larger than about 100
keV (and perhaps somewhat lower energies for electron loss), although target structure is
seen to play an important role for electron capture by low-energy protons. From the data
shown in Fig. 22, one can obtain an appreciation for the broad range of particle energies
and target species that have been investigated for protons and neutral hydrogen. A similar
plot for other ions would be much less complete; fewer targets have been investigated and
a more limited range of particle energies explored.
8. MULTIPLE IONIZATION
Interactions involving electrons and heavy ions can lead to multiple ionization of the
target atom or molecule. For example, ionization of an inner shell of an atom can result in
subsequent emission of one or more Auger electrons as the excited atom relaxes to the
ground state. This leads to two or more electrons, correlated in time and space, being
emitted in the immediate region of the original point of ionization. The correlation
involving multiple electrons produced by a single ionizing event can have a strong
inuence on subsequent chemical reactivity of the products of energy deposition.
Although inner-shell ionization cross sections are well known, the consequence of multiple
ionization is generally neglected in models of chemical kinetics because inner-shell
ionization cross sections are generally several orders of magnitude smaller than outer
shell ionization, i.e., multiple ionization via inner-shell ionization is a rare event.
On the other hand, the study of Auger electron spectra has been a productive means
of gaining information on the extent that multiple ionization occurs simultaneous with the
production of inner-shell ionization, i.e., the simultaneous ejection of outer-shell electrons
accompanying inner-shell ionization. When outer-shell vacancies exist in an atom or
molecule that is also ionized in an inner shell, the Auger transitions initiated in the inner
shells are shifted in energy by the presence of these outer-shell vacancies and these shifts
can be detected in the Auger spectra [74,75]. In fact, for collisions of high-energy heavy
ions, the degree of multiple ionization can provide such extreme shifts in the Auger line
energies that the normal spectral shapes are replaced with a statistical distribution of
transition energies [76]. Although Auger spectra provide indirect information on the
amount of multiple outer-shell ionization that accompanies inner-shell ionization, it
cannot give a good indication of the overall yields of multiple ionization because a sizable
fraction of the multiple ionization does not involve inner-shell ionization processes, but
occurs from direct ionization of the outer shell electrons.
As discussed above, heavy charged particles, particularly multiply charged heavy
ions, have a relatively large probability for inducing multiple ionization involving outer, as
well as inner, shells. For ions that carry several electrons interacting with a target atom, or
molecule that also have several bound electrons, multiple ionization may be the rule rather
than the exception. Such a collision can be represented as
A
q
B ! A
qj
B
i
i je
; 41
where the collision results in the capture of j electrons by the projectile and ionization of i
electrons from the target. Because of the multiple interactions between the nuclei and
electrons of the projectile and target, the theoretical treatment of such systems is generally
approached statistically [77].
The most detailed experimental information describing multiple ionization has been
obtained through the study of recoil target ion states in coincidence with selected projectile
states. To fully investigate the system would also require measurements of the electron
spectra in coincidence with post collision projectile and target charge states; however, such
experiments are extremely dicult. Therefore the general experimental focus has been on
the measurements of recoil charge state in coincidence with the selected projectile charge
state. Results of a coincidence study by DuBois [17,78] of the multiple ionization of a neon
target by proton and helium ions are shown in Fig. 23. The signicantly greater degree of
double and triple ionization of neon by He ions relative to that by protons is clearly
evident. At a few hundred keV, the contribution of double ionization reached more than
25% of that for single ionization; this is much greater than could be explained by
contributions from Auger cascades following inner shell ionization. For higher Z target,
the contributions from multiple ionization are even greater, reaching 50% for ionization of
Kr by He
+
. Only limited data exist for studies of multiple ionization of molecular targets,
and these studies are further complicated by the fact that molecules undergo a many
Figure 23 Cross sections for single, double, and triple ionization of neon by singly charged hy-
drogen and helium ions. (From Refs. 17 and 78.)
possible avenues of dissociation following ionization. In addition, coulomb explosions
can occur following multiple ionization that can disrupt molecular bonds and have severe
consequences on the subsequent radiation chemistry. Clearly more data is needed to
evaluate this important mechanism of ionization for heavy charged particles.
There is a wealth of fundamental information available on the interaction of fast
charged particles with atoms and molecules. Secondary electron distributions resulting
from ionizing collisions are well understood for incident bare projectiles and a few simple
dressed ions and neutrals. Even where a quantitative understanding of the collision is not
feasible, the basic features of the interactions are understood, making it possible to make
educated guesses as to the important parameters of the processes of energy loss. Still our
understanding and application of many of the known processes is limited. We are
particularly challenged to quantitatively describe the secondary electron spectra for
dressed ions and neutrals. We have only limited information on multiple ionization and
its consequences in radiation chemistry. There is a wealth of information in hand and a
plethora of questions remaining to answer.
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4
Modeling of Physicochemical and Chemical
Processes in the Interactions of Fast Charged
Particles with Matter
Simon M. Pimblott and A. Mozumder
1. INTRODUCTORY REMARKS
In Chapter 2 of this book, the energy transfer interactions of fast charged particles with
matter were discussed from the viewpoint of the incident particle. This chapter will describe
and examine the consequences of energy deposition in matter with the goal of providing an
understanding of the physico-chemical and chemical processes involved.
Energy deposition in a molecule is a necessary precursor to radiation-induced
transformations (see Sec 1.1 for a similar statement for photochemistry). In most situations,
especially in condensed media, the deposited energy is localized and available for physical
and chemical transformations. A sequence of correlated and localized energy loss events,
frequently in electronic form, may be termed a track. The incident particle generating the
track may suer occasional changes in direction, due mainly to elastic scatterings. This
eect becomes increasingly important as the particle slows down. At rst, the lost energy
appears in electronic form then generations of transformations may take place before a
particular radiation eect is observable. When there is sucient deposited energy,
ionization ensues and, frequently, secondary ionization and excitation will also occur.
These correlated events are localized in the vicinity of the primary interaction. For low
linear energy transfer (LET) radiations, the primary energy loss events are well separated.
The cluster of ionizations and excitations associated with each primary event is called a
spur, and on a certain timetable and in a certain chemical sense these clusters develop
independently. For high-LET radiations, the spurs of a track coalesce to form a more
continuous, cylindrical distribution. The thrust of this chapter is concerned mainly with
spur and track reactions. However, in conformity with the general aim and purpose of this
book, it should be remembered that the arguments are not limited to radiation chemistry
but can and should be extended to other applications (such as radiation biology and certain
industrial applications, etc.). One restriction is that the discussion will be chiey concerned
with condensed phase phenomena, although sometimes reference will be made to gas-phase
eects for the sake of comparison.
The organization of this chapter is as follows. In the following section, Sec. 4.2, the
elastic and inelastic interaction cross sections necessary for simulating track structure (ge-
ometry) will be discussed. In the next section, ionization and excitation phenomena and
some related processes will be taken up. The concept of track structure, from historical idea
to modern track simulation methods, will be considered in Sec. 4.4, and Sec. 4.5 deals with
nonhomogeneous kinetics and its application to radiation chemistry. The next section (Sec.
4.7) describes some application to high temperature nuclear reactors, followed by special
applications in low permittivity systems in Sec. 4.8. This chapter ends with a personal per-
spective. For reasons of convenience and interconnection, it is recommended that appro-
priate sections of this chapter be read along with Chapters 1 (Mozumder and Hatano), 2
(Mozumder), 3 (Toburen), 9 (Bass and Sanche), 12 (Buxton), 14 (LaVerne), 17 (Nikjoo), and
23 (Katsumura).
2. INTERACTION CROSS SECTIONS
In the interaction of fast charged particles with matter, the averaged macroscopic quantities
related to radiation physics can be evaluated from cross-sectional information that is of
limited complexity. For instance, the stopping power, which is the energy-weighted integral
over the inelastic collision cross section, can be computed fairly accurately using fairly ap-
proximate treatments (see Sec. 4.2.2). Bohrs theory is a prime example of such an approach.
On the other hand, chemical and other eects may depend on a specic excited or ionized
state of a molecule arising from a particular energy deposition event and on the local track
geometry. Elucidation of such eects therefore requires more accurate cross-sectional infor-
mation. Furthermore, because of the generation of copious low-energy secondary electrons,
the elastic and inelastic collision cross sections for these interacting particles are always sig-
nicant, even if the incident primary particle is highly energetic.
As an incident radiation particle slows down, various track processes occur with
sometimes several processes occurring simultaneously. Initially, electronic excitation dom-
inates inferior vibrational and rotational excitation. All the time, elastic collisions delineate
the track geometry. For the purpose of track simulation, it is often convenient to think in
terms of a collision mean free path, which is inversely related to the cross section. The basic
requirement for realistic simulation is then a comprehensive set of inelastic and elastic col-
lision cross sections for energetic (heavy) ions and for electrons over a wide span of energy.
In most cases, a doubly dierential cross section in energy and angle is sucient, but in cer-
tain cases, where detailed track geometry is not critical, a cross-section dierential in energy
is adequate.
2.1. Cross-Sections for Track Structure Simulation
Despite the fact that Bohrs stopping power theory is useful for heavy charged particles such
as ssion fragments, Rutherfords collision cross section on which it is based is not accurate
unless both the incident particle velocity and that of the ejected electron are much greater
than that of the atomic electrons. The quantummechanical theory of Bethe, with energy and
momentum transfers as kinematic variables, is based on the rst Born approximation and
certain other approximations [1,2]. This theory also requires high incident velocity. At
relatively moderate velocities certain modications, shell corrections, can be made to extend
the validity of the approximation. Other corrections for relativistic eects and polarization
screening (density eects) are easily made. Nevertheless, the BetheBorn approximation
gradually breaks down at electron energies of about 500 to 1000 eV in most media of low
atomic number.
The basic input information used in most cross-section calculations is the dierential
dipole oscillator strength distribution (DOSD) introduced in Sec. 2.2.2 and 2.2.3. For
polyatomic molecules, this is a continuous density distribution f(e) such that the dipole
oscillator strength for transition energies between e and e+de is given by f(e)de. In terms of
the DOSD, the total number of electrons receiving any energy transfer, the eective mean
excitation potential, the mean energy loss during a collision, and the mean excitation energy
for straggling [3] are given by
Z
e

_
e
max
e
0
fede
Z
e
lnI
e

_
e
max
e
0
feln ede
Z
e
e
_
e
max
e
0
efede
Z
e
elnI
_
e
max
e
0
efelnede
1
respectively [4]. In the above integrals e
0
is the lowest excitation potential of the molecule and
e
max
is the maximum energy transfer that is kinematically permissible. Because the incident
and ionized electrons are indistinguishable, e
max
virtually equals one-half of the incident
energy E, if that is large compared with the binding energy B. Otherwise, it should be taken
as
f
(E+B)/2. With known values of Z
e
, I
e
, q, and I, the electron stopping power at
relatively low incident energies may be expressed in the form [5]:
Selectron Z
e
ln
_
mv
2
I
e
~ e=8
_
_

e
2E
ln
4 eE
I
_ _
2
When E is suciently large that almost all the oscillator strength is contained within e
max
,
Z
e
and I
e
approach the limiting values of Z and I, respectively, in which case Bethes
nonrelativistic formula is recovered. Comparing Eq. (2) with Eq. (2.2.7), which includes
relativistic, shell, and density corrections, reveals that, as is stands, Eq. (2) does correct for
the energetically inaccessible states in the Bethe theory and therefore may be used at inter-
mediate electron energies. However, it is still limited to nearly zero momentum transfer in
collision kinematics. Ashley [6,7] has extended the use of the DOSDspectrumto account for
the nonvanishing momentum transfer by a quadratic approximation in the energymomen-
tum plane. It is better represented by the imaginary part of the reciprocal of the dielectric
response function e( q,x), where ,q and ,x are the momentum and energy losses, respec-
tively, in the collision process. Ashleys procedure involves replacing Im(1/e( q,x)) by
Im(1/e(0,x,q
2
/2m)). The relationship between the reciprocal dielectric response func-
tion and the DOSD has been discussed in Sec. 2.2.4 and is reproduced here with a slight and
obvious change in notations, viz. Im(1/e(0,x)) =(h
2
e
2
NZ/2m)f(e)/e, with e =,x. Ashleys
approximation has been well documented in a number of cases, including C and the metals
Al and Cu, and has been found to be accurate. Its most frequent application has been to
liquid water for relatively low energy electrons and protons [8,9].
Following Ashleys procedure and using the DOSD, f(e), the inelastic mean free path
K
i
for electronic excitation and ionization may be given by [8]
K
1
i
vN
_
e
1
feLe=Ede 3
here v = 2pe
4
/mv
2
, s = (12a)
1/2
and
La a
1
ln
1 a s1 a s
1 a s1 a s
_ _

2
1 a
F arcsin
s
1 a
_ _
;
1 a
1 a
_ _
Here F denotes an elliptic integral of the rst kind in Legendres normal form [10]. The
corresponding stopping power equation may also be expressed in a closed form[8] and when
expanded in powers of e/E , the lead term generates Bethes nonrelativistic result for the
stopping power for an electron. For the purpose of track simulation, the desired quantity is
the cumulative inelastic cross section of an event with energy loss less than e, which is given
by
rE; e N
1
K
1
i
v=E
_
e
e
0
f eVMe=E; eV=EdeV
_ _
4
in Ashleys approximation, where
Mb; a
1
a
ln
b a1 a b
b1 b
_ _

2
1 a
F arcsin
1 a 2b
1 a
_ _
;
1 a
1 a
_ _
The density of the actual energy loss is, of course, the derivative of the expression in Eq. (4)
The Ashley approximation greatly enhances the validity of the computed cross section for
electronic excitation. However, as only the DOSD is used, excitations to states that are
dipole forbidden are not included. This may not be a serious limitation unless the incident
energy is very low. An additional advantage of the approximation is that it is conveniently
used in the condensed phase.
2.2. Vibrational and Elastic Collision Cross Sections
For vibrational excitation under electron impact in the gas phase, experimental measure-
ments are generally available and are usually more reliable than calculation. In the case of
gaseous water, an almost complete compilation by Hayashi [11] is available in the all-
important lower energy regime. Hayashi decomposed the total vibrational collision cross
section into three components: r
v
1
,
v
3
for the v
1
and v
3
stretching modes, which are virtually
indistinguishable; r
v
2
for the v
2
bending mode; and r
w
for the balance. For polyatomic
molecules, rotational excitation involves very little energy relative to electronic or vibra-
tional excitation. In any case, experimentally these events cannot be distinguished from
elastic collision and are included with them in cross sections. Cross-sectional data for
vibrational excitation are of very limited availability in the condensed phase. Because inter-
nuclear forces are much stronger than the intermolecular forces, it is generally believed that
condensation does not eect vibrational cross sections a great deal and gas-phase values are
frequently used to represent the liquid in simulations. A detailed description of the cross
sections for electrons in liquid water is presented in Ref. 9, where the relevant cross sections
have been quantied for incident electron energy in the interval 10 eV to 100 keV.
Elastic collision cross sections are important for track simulation and dierential cross
sections are needed to calculate angular deviation in the track trajectory. Pimblott et al. [9]
have given an elaborate analysis for gaseous water and compared the results with the ex-
periments of Katase et al. [12]. In brief, the total elastic cross section
r
el
2p
_
p
0
dr=dhsinhdh
is well represented by the Moliere form for the dierential cross section, viz. dr/dh=
(Z
2
+Z)e
4
/( p
2
v
2
(1cosh+2g
2
)), where Z is the number of electrons in the molecule, p is the
electron momentum at velocity v, and the screening parameter, g, is a carefully chosen
parameter. Grosswendt and Waibels [13] choice for g is
g Z
2=3
1:64 0:0825 lnmc
2
T
_
=TT 2
where T is electron kinetic energy in units of mc
2
. This represents the total elastic cross
section well but, unfortunately, does not match the experimental dierential cross sectionfor
water. The analytical formula gives too little scattering in the forward direction, and it results
in a nearly isotropic distribution. Therefore Pimblott et al. [9] chose to t the dierential
experimental elastic cross sectionwithafourth-order polynomial a
0
+a
1
h+a
2
h
2
+a
3
h
3
+a
4
h
4
,
in which the a-coecients themselves were tted, as a function of energy, with another
fourth-order polynomial. The nally tted cross section agreed with experiment quite well. It
should be emphasized that the tting was done for the gas phase of water. The use of these
cross sections to represent liquid water is questionable, but there are no experimental
measurements available. The approximation has been justied by the belief that condensa-
tion does not aect the elastic collision cross section a great deal as these processes are
Figure 1 Electron energy dependence of the inelastic collision probability, r
inelastic
/(r
inelastic
+
r
elastic
), in liquid water (A) and the probability of an inelastic collision causing ionization, r
ion
/
(r
ion
+r
ex
), in gaseous (B) and liquid (C) water.
dominated by interaction of the electron with nuclear charges. While this may be true for
polyatomic molecules, it is well known that the elastic collision cross sections of atomic
liquids can be very dierent fromthose in the gas phase due to correlation eects represented
by the structure factor. In any event, it is customary to use the gas-phase elastic cross sections
in the condensed phases of molecular compounds for track simulation purposes.
For the purpose of track simulation, it is necessary to know whether the next realized
collision would be inelastic, and if it is, then either the collision would result in ionization or
in the production of a molecular excited state. The probabilities of these processes are given
by r
inelastic
/(r
elastic
+r
inelastic
), where r
elastic
and r
inelastic
are the cross sections for elastic and
inelastic collisions, and r
ion
/(r
ex
+r
ion
), where the cross sections for molecular excitation
and ionization are denoted by r
ex
and r
ion
, respectively. These probabilities for water in the
gaseous and liquid phases are shown as a function of electron energy in Fig. 1. The
probability of an inelastic process is virtually independent of the phase, although there is a
strong dependence on electron energy. On the other hand, the ionization probability de-
pends both on the phase and on the electron energy, with more ionization occurring in the
liquid phase at any electron energy.
3. IONIZATION, EXCITATION, AND RELATED PHENOMENA
The rst excitation potential of a polyatomic molecule is generally unambiguous. For
ordinary molecules it usually corresponds to transitions in the UV or in the far UV. The
excited molecule, either in the rst or in a higher excited state, may undergo prompt
dissociation, or fast internal conversion to states of the same multiplicity or convert,
relatively slowly, to states of dierent multiplicity by intersystem crossing. Kahsas rule
applies in most cases, signifying that the conversion to the state of lowest energy, singlet or
triplet, is very fast and further transformations occur relatively slowly. Occasionally, the
excited molecule will undergo a radiative transition resulting in the emission of a photon.
This process generally has a low probability, except for aromatic molecules where the
probability can be signicant. (Of course, the probabilities of the various outcomes, once the
excited molecule is formed, must add up to unity.) When the excited state is formed by the
absorption of a single photon, the probabilities are referred to as quantumyields. If the state
results from the absorption of n photons then the quantum yield is, by denition, that
respective probability divided by n.
Excited states can be formed by a variety of processes, of which the important ones are
photolysis (light absorption), impact of electrons or heavy particles (radiolysis), and, espe-
cially in the condensed phase, ion neutralization. To these may be added processes such as
energy transfer, dissociation from super-excited and ionized states, thermal processes, and
chemical reaction. Following Brocklehurst [14], it is instructive to consider some of the direct
processes giving excited states and their respective inverses. Thus luminescence is the inverse
of light absorption, super-elastic collision is the inverse of charged particle impact excitation,
and collisional deactivation is the inverse of the thermal process, etc.
The term ionization may refer to dierent processes depending on the context. For
radiation eects in the gas phase, it usually implies the removal of the least bound electron to
innity. Such a theoretical denition is not feasible in the condensed phase and it is necessary
use a heuristic or operational procedure. Thus, in liquid hydrocarbons, one may use the
electron scavenging reaction or a conductivity current to quantify the electrons liberated
from molecules. It has only been possible to extrapolate the conductivity current at a low
irradiation dose and at a relatively low external eld to saturation in the cases of liqueed
rare gases (LAr, LKr, and LXe) so that an unequivocal meaning to ionization may be
accorded [15].
The ionization potential is the minimum energy required to remove an electron from a
molecule, and as such it may be dened uniquely in the gas phase. Even so, as rst pointed
out by Platzman, ionization is not a certainty when that amount of energy is supplied to the
molecule. In super-excited states, ionization for polyatomic molecules is in eective
competition with dissociation into neutral fragments. At the same time, a small amount of
ionization may occur at energies a little below the ionization potential by a variety of
secondary processes. This blurring of the boundaries gives rise to the concept of ionization
eciency, which is the experimental ratio of the photoionization cross section to the
photoabsorption cross section. This eciency can be given a probabilistic interpretation
if it is assumed that once an excited state is formed its eventual fate is independent of the
process by which it was formed. In this sense, once the ionization eciency g
i
of a given state
is known, the cross sections for ionization and excitation may be given by g
i
r and (1g
i
)r,
respectively, where r is the cross section of production of that state either by photo-
absorption or by the impact of charged particles. This, of course, is true only when there is no
other channel for energy disposal, such as nonradiative transition to the ground state. In the
case of water in the gas phase, where the ionization potential is well established at 12.6 eV,
the ionization eciency, as a function of photon energy, shows a series of maxima and
minima until it asymptotically approaches unity at
f
20 eV [16]. This dependence implies
that the eciency of ionization depends not only on energy but also on the quantum nature
of the state reached by the absorption of a specied amount of energy.
Closely associated with the ionization potential, but distinct from it, are the W-value
and the appearance potential. The minimumenergy necessary to observe the production of a
particular ion out of a given molecule is called its appearance potential (see Ref. 2, p. 72). As
this is an experimental quantity without reference to the state originally produced, there has
been considerable confusion in the literature between the ionization potential and the
appearance potential in the liquid phase. In Sec. 4.3.2, a clarication is attempted for the
special case of liquid water. The W-value refers to the gross average energy needed to create a
single ionization in the medium, whether primary or secondary. It is greater than the
ionization potential, because of energy wastage in various nonionizing events, viz., pro-
duction of excited states, delivering energy to subexcitation electrons and to the resultant
positive ions, etc. A more detailed discussion will be found in Sec. 2.3.3.
3.1. Photoionization and Electron Impact Ionization
Photoionization is the process by which an electron is removed to generate a positive ion by
the absorption of light. Arelated process in which an electron is removed froma negative ion
to produce a neutral entity by light absorption is called photo detachment. The inverse of
photoionization is radiative capture of an electron. Applying microscopic reversibility to the
direct and inverse processes, the respective cross sections of photoionization (r
i
) and
radiative capture r
r
may be related by detailed balance as, r
i
/r
r
=(2x
f
/x
i
)(mc
2
T/h
2
m
2
),
where m is the frequency of light, and x
f
and x
i
are the statistical weights of the nal and
initial states, respectively. The factor 2 represents the spin degeneracy. Asimilar relationship
may be expected between the photo detachment and electron attachment cross sections.
These are very useful when one or another process is not easily amenable to experimental
investigation. It should be noted that the ionization cross sections are usually smaller than
the respective photoabsorption cross sections to which they are related by the ionization
eciency.
Ionization by a charged particle or by electron impact is a special inelastic collision
process in which molecular ionization occurs and the ejected electron carries the residual
energy. The basic cross section is still given by the BetheBorn theory as was used in Sec. 2.2
for stopping power and in Sec. 2.3 for secondary ionization. It should be noted that the
complete description of the impact ionization process requires a vefold dierential cross
section: one in the ejected electron energy and two each for the angular distributions of the
ejected electron and the primary particle. Such detailed information is rarely available
experimentally. Furthermore, the approximations used in the theory break down more
easily when higher order dierential cross sections are used. In radiation science, one is
frequently concerned with the total number of ionizations. As such, a singly dierential cross
section in ejected electron energy is sucient. For track simulation, a cross-section further
dierential in the angle of the ejected electron is necessary. However, in the more important
case when the energy of the secondary electron is much greater than the ionization potential,
a nearly classical relation between the ejected electron energy and angle can be invoked. In
any case, it should be emphasized that the ionization cross section, dierential in energy,
such as represented by Eq. (2.10), implies that ionization is a certainty once the deposited
energy exceeds the ionization potential. Because of the existence of super-excited states,
these cross sections must be multiplied by the ionization eciency factor. Presently, the only
useful source for this ionization eciency is experiment in the far UV. Even then, it is still
necessary to assume that the eciencies remain valid for the dipole-allowed states reached
by charged particle impact.
Under electron impact ionization, when the energy transfer greatly exceeds the orbital
ionization energy, the process resembles a Rutherford-type collision between two nearly free
electrons. On this Mott [17] imposed the condition of indistinguishability of the outgoing
electrons and obtained in the nonrelativistic limit
dr=dE
Mott
4pa
2
0
R
2
=T
_ _
i
n
i
W
2
i
W
1
i
T E
1
T E
2
_ _
5
where the same symbols are used as in Eq. (2.10). The second termwithin the brackets on the
right-hand side of Eq. (5) represents the interference between direct and exchange scatter-
ings. A manifestly relativistic treatment of the process has been given by Moller [18], how-
ever, with the caveat that in the extreme relativistic case and for a large angle scattering,
energy loss in the radiative process may not be negligible [19].
A wide variety of chemical reactions can occur following ionization or excitation of
a molecule in both gaseous and condensed phases. These may be of uni-molecular or bi-
molecular nature, initiated by electrons, ions or by the transformations of excited or ionized
molecules. These reactions include, but are not limited to, dissociation, elimination of atoms
and smaller molecules (H, H
2
, etc.), transfer of H
+
, H, H
2
, H
, and H
2
, fragmentation, ion-
molecule reaction, luminescence and energy transfer, neutralization, chain reaction, con-
densation, and polymerization, etc. These reactions will not be reviewed in this chapter but
may be found elsewhere in this book. A brief summary is also found in Chapters 4 and 5 of
Ref. 2. In the next section, some features of yields and mechanisms following excitation and/
or ionization in the liquid phase are discussed with special reference to water.
3.2. Condensed Phase: Yields and Mechanisms
The diculty of providing a theoretical denition of ionization in the liquid akin to that in
the gas phase has already been discussed. In practice, any available reaction that mimics that
of a free electron can be taken as an operational denition of ionization. These include
scavenging, attachment (dissociative or nondissociative), and other reactions of the
electron, as well as generation of solvated electrons in polar liquids and of free electrons
in nonpolar liquids. In some hydrocarbon liquids, careful extrapolation of the yield of
scavenged electrons gives a total ionization yield which is not much dierent from the
corresponding ionization yield in the gas phase; however, this is not always true. Extrap-
olation of the free-ion yield at innite external electric eld strength is generally uncertain,
depending on an assumed form of the initial electron-ion separation distance, although in
many cases such extrapolated ionization yields have been rationalized with those obtained in
scavenging experiments.
In highly polar liquids, such as water, the situation is altogether dierent and until
recently, the mechanisms and the yields of ionization and excitation were controversial.
Although it has been known for a long time that the fates of the lower excited states of water
are the same in all phases, viz. dissociation into H+OH, or into H
2
+O, the calculated yields
in the liquid phase exceeded experimental determinations by as much as a factor of four
[20,21]. An ad interim rationalization in terms of fast cage recombination lacks realism in
viewof the open structure of liquid water. As for ionization in liquid water, a very small yield
is seen at 6.5 eV[22,23] and this threshold has been variously called ionization potential [23],
threshold potential [24], or appearance potential [21]. Sander et al. [24,25] have postulated
that the mechanism of ionization by which low energy processes give e
aq
is not due to direct

or auto-ionization but to optical charge transfer or to photo-induced electron transfer. A
concerted proton-coupled electron transfer mechanism was rst proposed by Keszei and
Jay-Gerin [26] with later experimental support up to 9.3 eV [27]. Sander et al. [24] suggest
that quasi-free electrons may not be produced in the liquid until the band gap energy,
estimated around
f
1012 eV is reached.
The early work on the photolysis of water was in the gas phase employing one photon.
The branching ratio of the photodissociation into H+OH and H
2
+O was reported by
McNesby et al. [28] as 3:1 at a photon energy of 10.03 eV. Ever since, that ratio has been
consistently revised in favor of the H+OH reaction with the nal result of Stief et al. [29]
giving 0.99:0.01 for 6.708.54 eVphoton energy and 0.89:0.11 for the interval 8.5411.80 eV.
In the absence of direct determination these ratios often are assumed valid in the liquid
phase. In the early work of Sokolev and Stein [30], mainly the photodissociation quantum
yield in liquid water was measured, but a small photoionization yield of
f
0.05 was
attributed to the process
H
2
O
aq
!
hv
H
2
O
aq
** ! e
aq
OH H
3
O
aq
In the sense that the hydrated electron may be formed by the reaction of an excited state with
a ground state water molecule, the above reaction may have some validity [27]. In some of
the earlier work the initial yields were directly determined from scavenger studies. Later
works, using mostly two-photon photolysis, have been extended to higher energies and have
yielded more accurate photodissociation and photoionization yields. These have been
recently summarized in Ref. 31. Briey, the time dependencies were determined in the pico-
and subpicosecond time scales from which the initial and escape yields were found using
either analytical or Monte Carlo methods for the recombination kinetics. Fig. 2 shows
the variation of the quantum eciencies of photodissociation (g
d
) and photoionization (g
i
)
in liquid water as a function of photon energy in which some earlier data are incorpo-
rated. The quantum eciency of nonradiative transition to the ground state, computed as
(g
nr
)=1g
d
g
i
, is also shown. It is signicant below 9 eV but was ignored in earlier
expositions. The photodissociation quantum yield is very low below 6.70 eV because of the
high probability of nonradiative transition to the ground state and again very lowabove 10.0
eV because of the high ionization probability. It therefore exhibits a peak at
f
8 eV. The
ionization probability in liquid water has been postulated to reach a near certainty at a
photon energy 11.7F0.2 eV (see Fig. 2 ). Therefore, in accordance with the analysis of
Sander et al. [24,25], the ionization potential in liquid water may be dened as the minimum
energy needed to generate a quasi-free electron in the band gap, and a value of 11.7 eVcan be
assigned to it [31]. Notice that, according to this denition, the existence of the superexcited
state is denied in liquid water as the ionization potential is dened with respect to the
ionization eciency approaching unity and this quantity does not have maxima or minima.
An approximate calculation of the ionization yield in liquid water for high energy electron
radiolysis, using the data of Fig. 2 and a simplied Bethe theory, gives a G-value (yield for
100 eV absorbed energy) of 1.0 at rst collision and a total G-value of 2 obtained from it by
heuristic energy balance [31]. The latter is in good agreement with a recent experimental re-
evaluation of Bartels and co-workers [32]. The computed dissociation yield, however, falls
short of the experimental value by more than an order of magnitude. Therefore not only is
there no need for invoking cage recombination, there is actually a need for an additional
channel for dissociation into neutral fragments. Such a process, called dissociative electron
attachment (DEA), is well known in the gas phase and appears as a compound resonance in
low temperature ice in the energy interval
f
515 eV [33]. The immediate product of DEA is
H
+OH, where H
carries most of the excess energy and is likely to detach the electron
quickly. The net result is an electron degraded in energy and a dissociated water molecule.
An estimate of the total dissociation yield ( G
f
0.8) based on this hypothesis seems to be
correct in the order of magnitude [31].
Figure 2 Variation of the quantum eciencies of photodissociation (g
d
), of photoionization (g
i
),
and of nonradiative transition to the ground state, g
nr
=1 g
d
g
i
, in liquid water as a function of
photon energy.
4. TRACK STRUCTURE
4.1. Historical Perspective
The spatial distribution of the energy loss events of a charged particle is usually referred to as
a track. This conceptual picture of a track is the backbone of the theoretical description of
radiation chemistry. Tracks are considered to have a transitory existence and exist so long as
permitted by the diusion and fast reactions of radiation-produced intermediates (ions,
electrons, and radicals). A large body of radiation-physical and radiation-chemical phe-
nomena requires track models for their elucidation, including (1) LET variation of product
yields; (2) energy loss in primary excitations and ionizations; (3) yield of escaped ions; (4)
radiation-induced luminescence; and (5) particle identication.
The statistics of the energy loss events and their spatial distribution along a track, and
its branches, denes the structure of a radiation track. The ensuing chemistry depends on
incident particle energy and particle quality (LET). In 1966, a rudimentary Monte Carlo
method was used by Mozumder and Magee [35] for the statistics of energy loss events by
high energy electrons in water, employing simplied Bethe cross section derived from a
dipole oscillator distribution, which in turn was synthesized from then known moments and
experimental constraints. Their calculation divided energy deposition events into three
groups as follows: (1) spurs (spherical entities, up to 100 eV); (2) blobs (spherical or el-
lipsoidal, 100500 eV); and (3) short tracks (cylindrical, 5005000 eV). This arbitrary clas-
sication has proven to be tremendously useful and extremely robust in modeling radiation-
chemical kinetics. The track structure calculation showed that the energy partition between
the three track structure entities is a strong function of incident electron energy, dividing
approximately as the ratio of 0.64:0.12:0.24 in the spur, blob, and short track fractions for
60
Co-g irradiation. Recently, a more sophisticated calculation based on improved cross-
section methodology employing a realistic dipole oscillator distribution for liquid water has
provided an improved estimate of the ratio, 0.75:0.12:0.13, between the spur, blob, and short
track fractions [36].
The reaction of the radiation-induced radicals and ions comprising a track is signi-
cant in the condensed phases and the observed chemistry reects the competition between
the diusive relaxation of the track structure and the intra-track reaction. By contrast, in the
gas phase the reactants are widely dispersed at any reasonable dose and LET, and the in-
termingling of inter- and intra-track reactants gives a homogeneous character to the reac-
tions. The rst nonhomogeneous diusionreaction treatment of the radiation chemistry
of liquid water was proposed by Samuel and Magee [37] to explain the relative forward yield
as a function of LET. (Forward yield means the yield of observable molecular product
against radical yield, where the latter is estimated as the yield of scavenger reaction at a small
scavenger concentration.) Their simple analysis used a one-radical model, which made no
distinction between H and OH. Explicit consideration of reaction with homogeneously
distributed scavengers within the context of a one-radical-species model was later intro-
duced by Ganguly and Magee [38].
4.2. Track Structure Simulation
Track structure simulation has found application in many areas of radiation research since
the pioneering studies of Mozumder and Magee [35]. These studies all employ essentially the
same type of approach, a collision-to-collision modeling of the trajectory of the primary
radiation particle and of its daughter secondary electrons, with the most signicant dier-
ence between dierent calculations being the interaction cross sections used to describe the
various inelastic and elastic processes. The attenuating medium is usually treated as a
homogeneous continuum. The basic methodology for fast electrons is as follows: The
primary electron has an energy E and is at point z traveling in a dened direction. The
distance the radiation particle travels before its next collision, Dz, has a Poisson distribution
with a mean free path,
total
, which is dened by the total cross section, r
total
, for elastic and
inelastic processes, i.e.,
L
total
qr
total
1
qr
elastic
r
inelastic
1
6
where q is the number density of molecules. Consequently, the distance between two
consecutive collisions is obtained by the inversion method sampling from the probability
distribution function
PDz; L
total
1 exp Dz=L
total
7
and employing a uniformly distributed random number, U, in the range (01). Having
determined the distance traveled between collisions and knowing the direction of travel, the
position of the primary electron is modied to z
new
. The elastic and inelastic cross sections
(r
elastic
and r
inelastic
) comprising the total cross section are now used to determine the na-
ture of the collision by comparing a second uniformly distributed random number with
the probability of an inelastic collision, i.e., r
inelastic
/(r
elastic
+r
inelastic
). If the event is in-
elastic, the type of inelastic event is determined in a similar manner from the cross sections
for ionization (r
ionization
), excitation (r
excitation
), and the inferior energy loss processes
(r
vibration
), i.e.
0 <U <r
ionization
=r
inelastic Z
ionization
r
ionization
=r
inelastic
<U <r
ionization
r
excitation
=r
inelastic Z
excitation
r
ionization
r
excitation
=r
inelastic
<U <1
Z
vibration
The magnitude of the energy transfer, c, is calculated and the primary energy is reduced to
reect the loss, E
new
=Ec. For elastic events and for inelastic events that do not result in
ionization, the new trajectory of the electron is determined and the simulation proceeds in
the same manner. Following an elastic event, the direction of travel is determined from the
dierential elastic cross section, r
elastic
V (h,E), while excitation events are often assumed not to
alter the trajectory of the electron. If an inelastic collision causes an ionization event, the
ionization channel is determined using the cross sections appropriate for the dierent
ionization processes and the energy lost to the sibling positive ion is calculated. The
trajectories of the primary and the secondary electron are calculated from the kinematics.
When the energy of the daughter electron is smaller than a pre-dened cut-o energy, c
stop
,
this electron is not considered further, and the attenuation of the parent electron is
continued. If the energy of the secondary electron is greater than c
stop
, then its energy is
degraded until it is smaller than c
stop
before continuing the simulation of the parent electron
trajectory. The trajectory of the primary electron is followed until its energy drops below a
pre-dened cuto, c
nal
. Individual track simulations have many uses, for instance, in the
modeling of radiation chemical kinetics or quantifying radiation-induced DNA damage.
However, repeated realization of many dierent tracks is necessary to obtain statistically
signicant track averaged quantities such as stopping powers, ranges, and penetrations. The
mean values for many of these macroscopic parameters are available from alternative
calculations, but track structure simulation provides the best means for performing
sensitivity analyses and for accessing the distribution of a radiation parameter about its
mean value.
The simulation of a heavy ion track structure employs essentially the same method-
ology as described for energetic electrons; except that
the eects of elastic and inferior inelastic collisions are not signicant for ener-
getic heavy ions,
electron capture and loss by the primary ion must be considered, and
large numbers of electronic interactions may occur in close proximity.

The rst of these factors reduces the complexity of the simulation, but the second has en-
tirely the opposite eect as charge cycling events aect both the energy of the primary ion
and its inelastic collision cross section. While the proximity of energy loss events does not
aect the details of track structure simulation (at reasonable LET), it may cause signicant
complications in subsequent diusion-kinetic calculations due to the (potentially unphysi-
cally) high local concentration of radiation-induced reactants.
5. NONHOMOGENEOUS KINETICS
5.1. Transport and Reactions
As discussed, the passage of an ionizing radiation particle through a material leaves in its
wake a spatially nonhomogeneous track of highly reactive radicals and ions, which undergo
a characteristic nonhomogeneous chemistry. The ultra-fast chemistry of the radiation-
induced reactants is due to the relaxation of the nonhomogeneous distribution by the
diusion of the reactive radicals and ions and their diusion-limited reaction. Consequently,
the observed kinetics contains direct information about not only the short-time chemical
processes but also about the physical and physico-chemical processes that produce the
spatially nonhomogeneous distribution of reactants. Describing the chemistry immediately
following irradiation, and subsequent biological damage, requires a model that describes
not only the positions at which energy is transferred from the radiation particle to the
molecular medium, the physico-chemical consequences of each energy loss, and the local
spatial distribution of the radiation-induced reactants resulting from each ionization/
excitation event, but also the fast diusion-limited chemical reactions.
A number of dierent techniques have been developed for studying nonhomogeneous
radiolysis kinetics, and they can be broken down into two groups, deterministic and sto-
chastic. The former used conventional macroscopic treatments of concentration, diu-
sion, and reaction to describe the chemistry of a typical cluster or track of reactants. In
contrast, the latter approach considers the chemistry of simulated tracks of realistic clusters
using probabilistic methods to model the kinetics. Each treatment has advantages and lim-
itations, and at present, both treatments have a valuable role to play in modeling radiation
chemistry.
In the following two sections, deterministic (prescribed diusion and FACSIMILE)
and stochastic (random ights and IRT) approaches for the modeling of radiation chemical
kinetics will be described. Then representative calculations for simple aqueous systems will
be shown: The stochastic approach to modeling radiolysis kinetics is more physically
realistic than the primitive deterministic models; however, it is also more conceptually
advanced, requiring a more detailed (fuller) knowledge of the system under consideration.
5.2. Deterministic Kinetics
The rst serious attempt to treat the recombination kinetics of radiolysis was made by Jae
in 1913 [39] following Wilsons experimental demonstration of the columnar nature of a
radiolysis track [40,41]. The general approach outlined by Jae provides the basis for most
of the deterministic models used to model radiation chemistry. These models consider a
hypothetical average system characterized in terms of a nonhomogeneous concentration of
each species. Macroscopic laws are used to describe the diusion of the radiation-induced
particles and reaction is modeled using a deterministic rate equation dealing with net
changes in the average concentration. The result is a set of coupled diusion reaction
equations that are used to describe the nonhomogeneous kinetics. These equations have the
form [42],
@c
i
@t
D
i
r
2
c
i

k
ij
c
i
c
j

k
mn
c
m
c
n
8
where D
i
and c
i
are the diusion coecient and spatially dependent concentration of
species i. The rst term of the right-hand side of the equation represents the diusive
contribution to the evolution of c
i
, while the second and third terms represent removal
and production of i by reaction. The set of coupled equations is solved either by analytic
approximation or numerically.
The most frequently used analytic, approximate models for the fast kinetics in
radiolysis are based on an approximation suggested by Jae and known as prescribed dif-
fusion. The initial spatial distribution of the radiation-induced particles, their concentration
prole, is assumed to be Gaussian, and the kinetic analysis invokes the approximation that
reaction only aects the number of particles and not the form of the nonhomogeneous
spatial prole, which is therefore always Gaussian. The prescribed diusion approximation
relies upon the Greens function solution for the diusion equation being a Gaussian whose
variance develops as a linear function of time. This assumption is incorrect if the kinetics
is nonlinear, which is the case in real scenarios. In his pioneering study, Jae considered a
cylindrically symmetric columnar system, appropriate for high-LET radiation. In conven-
tional studies considering the kinetics of low-LET radiolysis, the system is usually described
in terms of a spherically symmetric typical isolated spur. The concentration prole of species
i is
c
i
r
N
i
2pr
2
i

3=2
expr
2
=2r
2
i
9
where N
i
is the number of i particles in the spur and r
i
2
is the variance of the Gaussian prole
and is time dependent, r = (r
2
(t = 0)+2Dt)
1/2
. Schwarz [42] extended the methodology to
a fully functional multi-radical model. By considering the species e
aq
, H+OH, H
3
O
+
, and
H
2
and employing an appropriate reaction scheme with realistic diusion and reaction rate
coecients, he was able to give a satisfactory (although not entirely accurate) description of
the variation of molecular and radical yields with LET, scavenger concentration, and pH.
In addition to the prescribed diusion approximation, several dierent numerical
treatments have been developed for solving the set of coupled diusion-reaction equations
(Eq. 9) [4345]. Most recent studies have been performed using a technique in which a
typical, average spur is used as a representation of the electron track. The spur is divided
into concentric shells as shown in Fig. 3. Each shell is suciently thin that the concentration
of reactants within the shell can be regarded as constant. Diusion takes place between
adjacent shells and reactions within a shell are modeled using deterministic rates. The
resulting set of coupled equations describing the diusion and the kinetics is solved using the
FACSIMILE implementation of the Gear algorithm [46]. The parameters dening the spur
for aqueous solutions have been optimized to match measured experimental yields in simple
scavenger studies [45]. The optimum energy of the spur, e
spur
, is 62.5 eV, which given the
approximate nature of this model is about the mean energy loss predicted by track structure
calculations.
5.3. Stochastic Kinetics
Stochastic diusion-kinetic treatments address the two fundamental aspect of the radiolysis,
i.e., the structure of the radiation track and the chemistry of the resulting spatially
nonhomogeneous distribution of radiation induced reactants. The track structure, describ-
ing the initial positions of the reactants, is usually prescribed by a simulation, as described
above, employing a collision-to-collision methodology with cross sections appropriate for
liquid water, then a diusion-kinetic simulation using either a computer intensive random
ight approach or the more elegant, but approximate, Independent Reaction Times
methodology is employed to model the radiation chemical kinetics.
Random Flight Simulation
The modeling of the radiation chemistry by diusion-kinetic simulation relies upon the
generation of reaction times frominitial coordinate positions. In a randomight simulation,
this calculation is performed in a brute force manner by mimicking the diusion and
encounter of the reactive particles. Several variants of the random ight simulation method
have been developed at dierent levels of sophistication, but all follow the same general
approach [4750]. Each simulation begins from a realizable conguration, generated at
random from the assumed spatial prole, either a spur or an idealized track structure. The
diusive trajectories of the particles are then simulated using a discretization of the
appropriate stochastic dierential equations. Reaction is modeled by overlap at the end
of a time step and/or by estimating the probability of encounter during a time step using a
bridging process. Each realization is continued until reaction is complete or a pre-dened
cut-o time is attained. Reaction kinetics is obtained by simulation of
f
10
4
spatial
congurations using dierent initial random number seeds. Each diusive jump has two
components. The rst represents the motion caused by the bueting of the solvent and the
Figure 3 Division of the typical spur into concentric shells in the deterministic treatment of spur
kinetics using the FACSIMILE algorithm.
second reects the drift caused by any force F. The jump is calculated using an Euler-type
discretization of the stochastic dierential equation, which gives change in a particles
position of
yr
i

2D
i
yt
_
N
3
0; 1
D
i
F
i
k
B
T
dt
where D
i
is the diusion coecient of the particle, yt is the length of the time step, and N
3
is a
three-dimensional normal random vector with unit variance. This simulation methodology
has been validated, for several types of idealized system, including radical spurs and ionic
spurs in both high and low permittivity solvents [47,48,51].
For neutral reactants the force F=0, and therefore [47]
dr
i

2D
i
dt
_
N
3
0; 1
When the particles are charged, the strong inter-ion forces modify the diusion. The
(Coulombic) force on ion i is then [48]
F
i
k
B
T
j
z
i
z
j
r
c
r
3
ij
r
ij
where z
i
is the charge on ion i, and r
ij
is the inter-ion vector. The Onsager distance, r
c
,
is the distance at which the potential energy of the Coulombic interaction of two unit
charges has magnitude k
B
T.
In the presence of an applied electric eld, E, the expression for the force on an ion is
further modied to [52]
F
i
k
B
T
j
z
i
z
j
r
c
r
3
ij
r
ij
z
i
eE
where e is the electron charge.
The majority of simulations reported in the literature use a xed time step, yt [48,50];
however, this treatment is computationally inecient. When the particles are well separated
the probability of encounter is small. Sophisticated methods have been developed, which
allow more ecient computation by incorporating variable time steps [47,49,51]. In these
treatments, the time step, yt, is determined by the proximity of the particles. The time step is
selected by one of two methods:
(i) so that the pair with the shortest inter-particle separation has a very small
encounter probability [47], or
(ii) so that the change in the inter-particle drift of every pair during the time step is
small [49,51].
In both treatments, the minimum time step becomes increasingly small as two particles
approach so a minimum time step, typically
f
10 fsec, has to be employed to ensure that
the simulation does not stall.
If a reaction is diusion-controlled then reaction occurs on encounter of two particles.
In a simulation employing nite time steps, a pair of reactants may encounter during a time
step and then separate before the end of the time step. This pair should have reacted, but
the reaction is not registered. Consequently, the modeled kinetics underestimates both the
rate and the amount of reaction. This problem of encounter during a time step can be
overcome using the conditional encounter probability for an interpolating bridging
process [53]. Two forms of bridging process have been developed: the Bessel bridge, which
assumes that the separation behaves as a Bessel process, and the Brownian bridge in which
the separation between the two particles is approximated by a Wiener process.
While many of the important reactions in radiation and photochemistry are fast, not
all are diusion-limited. The random ight simulation methodology has been extended to
include systems where reaction is only partially diusion-controlled or is spin-controlled
[54,55]. The technique for calculating the positions of the particles following a reecting
encounter has been described in detail, but (thus far) this improvement has not been incor-
porated in realistic diusion kinetic simulations. Random ight techniques have been suc-
cessfully used to model the radiation chemistry of aqueous solutions [50] and to investigate
ion kinetics in hydrocarbons [48,50,5658].
Independent Reaction Times Modeling
The IRT model has been developed in detail in a series of papers of Green, Pimblott and co-
workers and has been validated by comparison with full random ight simulations
[47,49,51]. The IRT treatment of the radiation chemistry relies upon the generation of
randomreaction times from initial coordinate positions from pair reaction time distribution
functions. A simulation, such as a random ight calculation, starts with the initial spatial
distribution of the reactants. The separations between all the pairs of particles are evaluated
Figure 4 Schematic representation of the IRT method for a four-radical spur.
and overlapping pairs are allowed to react. Reaction times for all the surviving pairs are
calculated from the reaction time distribution functions for the pairs as if they were in
isolation. (This approximation is an application of the independent pairs approximation that
is implicit in the DebyeSmoluchowski treatment of diusion limited kinetics.) The resulting
ensemble of times is then used to determine the times of subsequent reactions. When a
reaction occurs, any reactive products are positioned using an independent diusion
treatment [47]. New reaction times are determined from the appropriate rst passage time
distribution function and a modied ensemble of times is created. The simulation proceeds
until a predened time (usually 1 Asec) is reached or until no reactive particles remain. The
kinetics of the system is obtained by repeated realization using a dierent initial cong-
uration and dierent random number seeds. This technique is demonstrated schematically
for a four-radical spur in Fig. 4.
The IRT method was applied initially to the kinetics of isolated spurs. Such calcu-
lations were used to test the model and the validity of the independent pairs approximation
upon which the technique is based. When applied to real radiation chemical systems, iso-
lated spur calculations were found to predict physically unrealistic radii for the spurs,
demonstrating that the concept of a distribution of isolated spurs is physically inappro-
priate [59]. Application of the IRT methodology to realistic electron radiation track struc-
tures has now been reported by several research groups [6064], and the excellent agreement
found between experimental data for scavenger and time-dependent yields and the pre-
dictions of IRT simulation shows that the important input parameter in determining the
chemical kinetics is the initial conguration of the reactants, i.e., the use of a realistic ra-
diation track structure.
6. APPLICATION TO RADIATION CHEMICAL STUDIES
Investigation of the eects of radiation type and energy on radiation chemical kinetics using
a combination of experimental and stochastic simulation methods provides the most direct
insight into the nonhomogeneous diusion and reaction processes occurring in a radiation
track, which ultimately determine the damage caused by radiation. While the chemistry
induced by low-LET radiation has received considerable experimental and theoretical at-
tention, similar comparisons on the eects of high-LET radiation are lacking.
6.1. Gamma and Electron Radiolysis
The irradiation of water is immediately followed by a period of fast chemistry, whose short-
time kinetics reects the competition between the relaxation of the nonhomogeneous spatial
distributions of the radiation-induced reactants and their reactions. Avariety of gamma and
energetic electron experiments are available in the literature. Stochastic simulation methods
have been used to model the observed short-time radiation chemical kinetics of water and
the radiation chemistry of aqueous solutions of scavengers for the hydrated electron and the
hydroxyl radical to provide fundamental information for use in the elucidation of more
complex, complicated chemical, and biological systems found in real-world scenarios.
Hydrated Electron Kinetics
There is a large amount of experimental data on the radiation chemical yield of e
aq
,
including direct absorption measurements of the time dependence of the yield in deaerated
water [6673] and a variety of scavenger studies that have been used to determine the eect of
scavenging capacity, s (equal to the product of the scavenger concentration and the rate
coecient for the scavenging reaction, k[S]) on the scavenged yield of e
aq
[45]. Extrapolation
of the recently re-evaluated time dependence of e
aq
measured experimentally to the pico-

second time scale suggests a yield of e
aq
of 4.0F0.2 [32]. These data are compared with the

simulated kinetics of a 1-MeVelectron degraded by 10 keVin Fig. 5. The standard deviation
of the thermalization distribution of e
aq
that best reproduces the experimentally observed

kinetics is
f
5.2 nm. Notice that very little reaction occurs at times less than 0.1 nsec. The
short-time yield is primarily determined by the ionization yield and the amount of ultra-fast
recombination of the precursors to the hydrated electron, e
pre
, with the molecular cation,

H
2
O
+
. The precursors to the hydrated electron do not participate in signicant intra-track
chemistry in neat water.
In the IRT modeling of the radiation chemistry of water, the ionization yield is
determined by the track structure simulation: it is not a variable. In contrast, the thermal-
ization distribution for e
aq
, which represents the degradation of the electron energy from

E=c
nal
to solvation, is a variable in the diusion-kinetic calculation. The value obtained is
in agreement with estimates of Crowell and Bartels derived from picosecond laser study of
the multiphoton ionization of liquid water [74]. Furthermore, the mean distance is essentially
the same as the average thermalization distance,
f
8.3 nm, estimated by Monte Carlo
simulation of the energy loss of subexcitation electrons in solid water using the cross sections
for ice [75] and is similar to the mean thermalization lengths estimated by Konovalov et al.
from electron photo-ejection experiments in water, hl i = 6.08.0 nm [76]. (The thermal-
ization distances of Konovalov depend upon the initial electron energy, whereas the
radiation chemical spur width is for a distribution of energies.) The spur width derived by
stochastic simulation and from these experiments is considerably larger than obtained from
previous deterministic analyses of scavenger experiments, where r(e
aq
)
f
23 nm [42].
Figure 5 Decay kinetics of the hydrated electron. Experimental data: (....) [32]; ( ) [73].
IRT kinetics: ( ) r(e
aq
)=4.0 nm; ( ) r(e

aq
)=5.2 nm; ( ) r(e

aq
)=7.5 nm.
Precursors to the Hydrated Electron
The scavenging capacity dependence of the scavenged yield of e
aq
is shown in Fig. 6 [7782].

Comparison of the modeled chemistry with data fromexperimental scavenger studies shows
excellent agreement. The calculations reproduce both the absolute yields and the relative
variation as a function of scavenging capacity of the majority of the data. While Fig. 5 shows
that e
pre
is not signicantly involved in the observed intra-track radiation chemistry of pure

water, in concentrated aqueous solutions of e
aq
scavengers, scavenging reactions may take

place at early times. Two types of scavenging reaction may contribute to the observed
chemistry, scavenging of e
pre
and of e
aq
. Scavenger systems are commonly used to estimate

the yield of e
aq
in the radiolysis of water. Consequently, understanding the eects of

scavenging e
pre
is important. Fig. 6 compares calculations for several e

aq
scavengers. The
yields of N
2
from N
2
O solutions correspond to predictions from the Laplace transform of
the decay kinetics of e
aq
, and examination of the details of the IRTcalculations clearly shows

that the precursors of the hydrated electron do not inuence the chemistry. In nitrate
solutions, for e
aq
scavenging capacities less than 10

8
sec
1
, the (e
pre
+NO
3
) reaction does
not have an eect on the amount of electrons scavenged. At higher concentrations,
k(e
aq
+S)[S]
f
10
9
sec
1
, the scavenging of e
pre
has a statistically (although probably not

experimentally) signicant eect on the amount of electrons scavenged. This dierence
becomes more distinct as the concentration of NO
3
increases. The curve for the eect of

selenate concentration on the amount of electrons scavenged is shifted considerably from
those for the generic e
aq
scavenger N
2
O and for NO
3
. The shift reects the primary role that

Figure 6 Eect of scavenging capacity for e
aq
on the number of electrons scavenged in aqueous

solutions of nitrous oxide, nitrate, and selenate. Experimental data: nitrate(n) [77], (
x
) [78];
selenate(
) [79]; nitrous oxide(E) [80], (z) [81], (Y) [82]. IRT simulation: nitrate( );
selenate( ); nitrous oxide( ).
the reaction of e
pre
with SeO
4
2
plays in determining the amount of scavenging. Only in very
dilute solution is the reaction of e
aq
with SeO
4
2
dominant.
6.2. Light and Heavy Ion Radiolysis
Stochastic simulation methods have recently been developed for modeling heavy ion track
structures using collision cross sections appropriate for liquid water [83]. Realistic diusion-
kinetic calculations on the eects of high-LET radiations such as alpha particles and
accelerated light and heavy ions are scarce [8486], and the only system that has been
investigated thoroughly is the dependence of the Fricke dosimeter on radiation ion and
energy [86]. Fig. 7 compares the results of stochastic IRT simulations for track segments
with experimentally determined dierential yields [8789], showing excellent agreement for
energetic electrons and for nonrelativistic ions, including
1
H,
4
He,
12
C, and
20
Ne. The data
reveal a signicant eect of particle type and energy, which reects the competition between
intra-track reaction of the radiation-induced radicals, diusion, and scavenging. This
competition is modied by changes in the ion track structure. Examination of the underlying
Monte Carlo track structure simulations shows that the radial energy loss proles are similar
for ions with the same velocity/charge ratio and that
f
40% of the energy is initially
deposited within a water diameter of the track axis. The simulations demonstrate that LET
of the ionizing radiation is a poor parameter for characterizing the Fricke dosimeter, and the
Figure 7 Eect of ion energy on the response of the Fricke dosimeter. The solid lines and lled
points are the experimental data. ( ) labeled curves for
1
H,
4
He,
12
C, and
20
Ne ions [87]; ()
2
D(at E/2) [88]; (E)
4
He
2+
[88]; (z)
12
C [89]; (Y)
20
Ne [89]. The dashed lines joining the open points
represent stochastic IRT simulations for heavy ions, and the dotted line refers to calculations for the
complete slowing down of energetic electrons.
Figure 8 Eect of
1
H ion energy on the yield of N
2
from saturated N
2
O solution. Experimental
data: track average yield (
) [90]. IRT simulation: track segment yield (o); track average yield
( ).
Figure 9 Eect of radiation type and of scavenging capacity for e
aq
on the yield of NH
3
and N
2
from glycyl-glycine and N
2
O solutions, respectively.
observed chemistry is predicted more precisely by the square of the ratio of the particle
charge to its velocity.
There are almost no radiation chemical studies of the yields of the primary radiation-
induced species made with ions of well-dened energy. To develop a realistic, predictive
model for the eects of radiation it is important to chart the interplay between the various
physical and chemical factors aecting track structure and track kinetics for all of the
primary radiation-induced species, e
aq
, OH, H
2
, and H
2
O
2
. For instance, modeling of the
track chemistry of a heavy ion necessitates the simulation of track segments for ions of
dierent energy, followed by integration, as track segment yields are very dierent from the
track average yield except at high ion energies. A typical calculation of this kind is shown in
Fig. 8, which examines the production of N
2
from the
1
H ion radiolysis of aqueous nitrous
oxide solutions [90]. Astudy of this type is necessary for each calculated result in a scavenger
concentration study, such as Fig. 9, which compares recent experimental yields with
stochastic IRT predictions for the eect of the concentration of glycyl-glycine on the yield
of NH
3
and of nitrous oxide on the yield of N
2
from aqueous solutions irradiated with
60
Co
gamma rays and 5 MeV He ions [91,92]. The potential interplay of calculation with
experiment suggested by the data shown in Figs. 79 has many benets. In addition to
the accurate prediction of the eect of radiation quality on radiation-induced chemistry,
realistic kinetic modeling will enable the elucidation of the underlying physical and chemical
processes by analysis of the simulated track structures and the modeled interplay of diusion
and reaction.
7. APPLICATION TO HIGH-TEMPERATURE NUCLEAR REACTORS
There is a large amount of data on nonhomogeneous track chemistry of energetic electrons
at room temperature, and the track structure and diusion-limited kinetics are well param-
eterized. This wealth of knowledge contrasts with the limited information about the eects
of radiation on aqueous solutions at elevated temperatures. The majority of the studies at
elevated temperatures have been performed at AECL, Canada [93], or at the Cookridge
Radiation Laboratory, University of Leeds, UK [94]. These two groups have focused on
measuring the rate coecients of the reactions of the radiation-induced radicals and ions of
water. The majority of the temperature dependencies can be tted with an empirical
Arrhenius-type expression, k=A exp(E
a
/k
B
T ). This type of parameterization provides a
satisfactory estimate of the rate coecient, but it should not be taken to have any
mechanistic implications. Radiation-induced radicals are very reactive, and so most of their
reactions are close to diusion-controlled at room temperature. At elevated temperature,
however, deviations from diusion-control are apparent. Consequently, the temperature
dependence has to be described using two components, k
1
obs
=k
1
di
+k
1
react
, one for the
encounter process, k
di
, and one for the reaction process, k
react
. The temperature depend-
encies of the diusion coecients of the radiation-induced ions and of the water molecule
are partially known; however, the diusion-coecients of the neutral radicals are poorly
characterized even at room temperature. In the diusion-kinetic calculations, it has been
necessary to assume that these species have diusion coecients with the same temperature
dependence as the self-diusion of water.
The temperature dependencies of the yields of e
aq
, H, H
2
, OH, and H
2
O
2
following g
irradiation have been investigated using radical scavengers. The yields of the principal
reducing, e
aq
, and oxidizing, OH, radicals are quite well known and increase with increasing
temperature. There are some discrepancies between dierent experimental studies for H
2
;
however, the yield is either independent of temperature or increases slightly with increasing
temperature (<30% at 300jC). The yield of H atom is not accessible directly and can only
be obtained in conjunction with H
2
. The sum of the yields of H and H
2
is more or less
independent of temperature. The yield of H
2
O
2
appears to decrease with increasing
temperature in contrast to H
2
; however, there is no reliable information above 150jC. A
number of deterministic and stochastic calculations have investigated the gamma and heavy
ion radiolysis of water at elevated temperatures [9599]. For the most part these studies have
focused on the observable yields rather than the underlying track structures. The principal
eect of elevated temperature on the track structure of energetic electrons in water is due to
changes in the inter-event mean-free path. This property depends inversely upon the density
of water so increasing temperature increases the separation between intra-track energy loss
events. Consequently, (i) the dose distribution of the track is more diuse at elevated
temperatures than that at roomtemperature, and (ii) the spurs (clusters of radiation-induced
reactants) comprising the nonhomogeneous spatial distribution of reactants are more
isolated. Fig. 10 compares the dose distribution of a 1-keV electron at 25jC and at
300jC. The very apparent spreading of the track structure is signicant as chemistry in
clusters emphasizes stochastic eects and should therefore lead to increased recombination
Figure 10 Comparison of the dose distribution of a 1-keV electron at 25jC (dashed contours) and
at 300jC (solid contours). Dose in eV/nm
3
.
relative to molecular product formation. The reaction time for a pair of radiation-induced
reactants depends upon their separation, their transport properties, and the rate of reaction
upon diusive encounter. In addition, physical parameters, such as the relative dielectric
coecient and the density of water, have to be considered in calculations as they aect the
diusion-reaction kinetics by modifying the inter-ionic forces and the rates of processes
involving the solvent, i.e., water. Stochastic (and deterministic) radiation chemical kinetic
calculations have been made for gamma radiolysis of water over the temperature range 25jC
to 300jC, and the predictions have been compared with available experimental data for
gamma radiolysis. Agreement is found for all of the radiation-induced species and for the
combined yield of H and H
2
. For the radicals e
aq
and OH, the calculations quantitatively
reproduce the measured yields and their temperature dependence. The predictions of
stochastic IRT calculations, employing simulated fast electron tracks, for the yield of OH
radicals are compared with the available experimental data in Fig. 11 [100,101].
8. LOW PERMITTIVITY SOLVENTS
In contrast to liquid water, a detailed mechanistic understanding of the physical and chem-
ical processes occurring in the evolution of the radiation chemical track in hydrocarbons is
not available except on the most empirical level. Stochastic diusion-kinetic calculations for
lowpermittivity media have been limited to simple studies of cationelectron recombination
in aliphatic hydrocarbons employing idealized track structures [5658], and simplistic
deterministic calculations have been used to model the radical and excited state chemistry
[102]. While these calculations have been able to reproduce measured free ion yields and end
product yields, respectively, the lack of a detailed mechanistic model makes it very dicult
Figure 11 Eect of temperature on the yield of OH radicals from gamma radiolysis. Experiments:
(E) Kent and Sims [100], (n) Elliot et al. [101] Calculation: (solid line) IRT modeling using track
structure simulation.
to predict the eects of dierent types of radiation or to speculate on the eects of radiation
on uninvestigated systems.
Dierential dipole oscillator strengths are available for a large variety of gaseous
hydrocarbons, and for a limited number of liquids and solids. These data have allowed the
calculation of the condensed phase energy loss properties, including the cross sections for
inelastic collisions, of electrons and positrons in n-hexane, cyclohexane and benzene, and
in polyethylene and polystyrene [103]. Cross sections for elastic collisions have also been
evaluated using partial wave methods [104]. Recently, these inelastic and elastic cross sec-
tions have been successfully used in the stochastic diusion-kinetic simulation of the electric
eld dependence of the o-positronium yield in n-hexane [58], showing that positronium for-
mation involves reaction of the thermalized positron with electrons produced along the last
few hundred nanometers of its track-end, corresponding to several kiloelectronvolts of en-
ergy attenuation. More complex studies of radiation chemical eects in hydrocarbons are
necessary.
9. PERSPECTIVE
Over the last 15 years, stochastic methodologies for modeling the radiation chemical kinetics
of aqueous systems have made signicant progress, advancing from isolated spur studies to
58
Ni track chemistry simulations. The IRT methodology for modeling radiation and
photochemical kinetics is now used worldwide. Development of realistic models for track
chemistry is crucial to predicting radiation eects in complicated practical applications and
where experiments cannot be performed. However, the calculations for both low- and high-
LETradiation still suer froma number of deciencies. The physical, physico-chemical, and
chemical processes that occur in the radiation track on a subpicosecond time scale are not
well characterized despite recent advances into this time domain in laser irradiation studies.
A multi-faceted approach employing experiments in conjunction with Monte Carlo kinetic
modeling and electronic structure calculations is clearly desirable to elucidate fundamental
radiation chemical processes from their earliest stages.
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5
Interaction of Photons with Molecules:
Photoabsorption, Photoionization,
and Photodissociation Cross Sections
Noriyuki Kouchi and Y. Hatano
Tokyo Institute of Technology, Tokyo, Japan
SUMMARY
The absolute values of the photoabsorption, photoionization, and photodissociation cross
sections are key quantities in investigating not only the interaction of photons with mo-
lecules but also the interaction of any high-energy charged particle with matter. The
methods to measure these, the real-photon and virtual-photon methods, are described and
compared with each other. An overview is presented of photoabsorption cross sections
and photoionization quantum yields for normal alkanes, C
n
H
2n + 2
(n = 14), as a func-
tion of the incident photon energy in the vacuum ultraviolet range and of the number of
carbon atoms in the alkane molecule. Some future problems are also given.
1. INTRODUCTION
The interactions of photons with molecules are classied into absorption, scattering, and
pair production. In this chapter, photons of moderate energies, particularly in the vacuum
ultraviolet range, are discussed, and therefore only the absorption process is considered.
The absorption of a single photon by a molecule in the electronically ground state changes
its electronic state from the ground state 0 to a nal excited or ionized state j. Its transition
probability is expressed in terms of the optical oscillator strength f
j
[1,2].
The optical oscillator strength f
j
is expressed as
f
j
E
j
=RM
2
j
1
where E
j
is the excitation energy in the transition of 0!j, R is the Rydberg energy (R=
(1/2)(atomic units)=13.6 eV), and M
j
2
is the dipole matrix element squared in the transi-
tion of 0!j in atomic units. Note that f
j
is dimensionless. A set of E
j
and f
j
characterizes a
discrete spectrum. To discuss a continuous spectrum, one expresses the oscillator strength
in a small range of the excitation energy between E and E + dE as (df/dE)dE, and calls
df/dE the oscillator-strength distribution, or, more precisely, the spectral density of the
oscillator strength. Thus df/dE has the dimension of the reciprocal of energy. The quantity
df/dE is also dened for the discrete transition 0!j as
df=dE
j
f
j
d E
j
E
_ _
2
The integral of df/dE over a total space of E gives the total number Z of electrons in the
molecule under consideration,
m df=dE dE Z: 3
Equation (3) is known as the ThomasKuhnReiche (TKR) sum rule.
The oscillator-strength distribution df/dE is proportional to the cross section r
for the absorption of a photon of energy E, the so-called photoabsorption cross section.
Note that the excitation energy is equivalent to the photon energy. Explicitly, one may
write
rE 4p
2
aa
2
0
df
dE=R
4
where a is the ne structure constant and a
0
is the Bohr radius. Equation (4) is more
conveniently written as
rE 1:098 10
16
df
dE
_ _
5
where r(E) is expressed in cm
2
and df/dE in eV
1
.
The partial oscillator-strength distribution of a channel n, (df/dE)
n
, is also dened
and is related to the cross section of channel n following the absorption of a photon of
energy E, r
n
, by
r
n
E 4p
2
aa
2
0
df
dE=R
_ _
n
4V
and more conveniently by
r
n
E 1:098 10
16
df
dE
_ _
n
5V
where r
n
(E) is expressed in cm
2
and (df/dE)
s
in eV
1
. The channel n refers to, for example,
the ionization of a specied electron, formation of a specied product, and so on. The
summations of r
n
(E) and (df/dE)
n
over all channels give r(E) and df/dE, respectively, as
rE
n
r
n
E 6
df
dE

n
df
dE
_ _
n
7
Thus the quantum yield of channel n, g
n
(E), the number of times of channel n per
absorption of a photon of energy E, is expressed as
g
n
E
r
n
E
rE

df=dE
n
df=dE
8
The dipole matrix element squared for channel n in atomic units, M
2
n
, is given by
M
2
n

_
R
E
_ _
df
dE
_ _
n
dE 9
Note that E in the right hand side of Eq. (9) is not in atomic units.
As described in the Introduction of Chap. 1, a decisive step in the physical and physi-
cochemical stages of the interactions of any high-energy incident particles with matter,
in case it is composed of molecular compounds, is the collision of secondary electrons
with molecules in a wide energy range. Cross sections for the ionization and excitation of
molecules in collisions with electrons in the energy range greater than about 10
2
eV are well
elucidated quantitatively by the BornBethe theory [3]. This theory is also helpful for cal-
culating, at least roughly, these cross-section values further in the lower energy range.
According to the optical approximation, which was shown by Platzman [4] to be
based on the BornBethe theory, a radiation chemical yield of channel n, G
n
, may be
estimated from optical data as shown in the following equation:
G
n
100=W M
2
n
=M
2
i
_ _
10
where W is the mean energy (in eV) for the production of an ion pair, and M
2
n
and M
i
2
are
the dipole matrix elements squared for channel n and ionization, respectively. Because this
equation indicates that a radiation chemical yield is estimated from optical cross-section
data, it is concluded, therefore, that photoabsorption, photoionization, and photodisso-
ciation cross-section data of molecules are of great importance in understanding not only
the interactions of photons with molecules, but also those of any high-energy incident
particles with molecules [5].
There have been remarkable advances in synchrotron radiation research and related
experimental techniques in the range from the vacuum ultraviolet radiation to soft X-ray,
where the most important part of the magnitudes of these cross-section values is observed,
as shown below. Therefore, it is also concluded that synchrotron radiation can bridge a
wide gap in the energy scale between photochemistry and radiation chemistry. Such a
situation of synchrotron radiation as a photon source is summarized in Fig. 1 [5,6].
Fig. 1 shows the wavelengths of electromagnetic radiation from the infrared to the g-
ray ranges and corresponding photon energies. Characteristic X-rays,
60
Co and
137
Cs g-
rays, and vacuum ultraviolet light from discharge lamps are indicated by the arrows. The
shaded areas indicate the ranges for which photon sources, apart from synchrotron
radiation, are available and correspond to photochemistry and radiation chemistry.
In this chapter, we discuss the photoabsorption and photon-induced processes in
terms of r and r
n
(or g
n
), respectively.
In Fig. 2, the photoabsorption (r), photoionization (r
i
), and photodissociation (r
d
)
cross sections of CH
4
measured by Kameta et al. [7] are shown as a function of the incident
photon energy in the range 1024 eV. The electron conguration of the ground electronic
state of CH
4
in T
d
symmetry is [8,9,10,11]:
1a
1
2
..
inner shell
2a
1
2
..
inner valence
1t
2
6
..
outer valence
The vertical ionization potentials of the (1t
2
)
1
and (2a
1
)
1
ionic states are indicated in
Fig. 2, while that of the (1a
1
)
1
ionic state is far away from the range in Fig. 2. Kameta
et al. examined their photoabsorption cross sections r in terms of the TKR sum rule for
the oscillator-strength distribution df/dE, Eq. (3), following the conversion of r to df/dE,
Figure 1 Synchrotron radiation (SR) chemistry as a bridge between radiation chemistry and photo-
chemistry. The oscillator-strength distribution df/dE is shown as a function of wavelength k and
photon energy E. Note the relation E k = 1.24 10
3
, where E is measured in eV and k in nm. The
intensity of synchrotron radiation is also roughly shown, as are the energies of photons from several
line sources. VUV, EUV, SX, and HX stand for vacuum ultraviolet, extreme ultraviolet, soft X-rays,
and hard X-rays, respectively. (From Refs. [5,6].)
Figure 2 The photoabsorption (r), photoionization (r
i
d
) cross sections
of CH
4
as a function of the incident photon energy measured via the double ionization chamber and
synchrotron radiation as mentioned in Section 2.1. The values of r in the range below the rst
ionization potential were measured by the photon-beam attenuation method, using the ionization
chamber as a conventional gas cell. The bandpass was 0.1 nm, which corresponds to the energy
width of 32 meV at the incident photon energy of 20 eV. The vertical ionization potentials of the
ionic states involved are also indicated by the vertical bars [11]. (From Ref. [7]. Reprinted with
permission from Elsevier Science.)
Eq. (4). The result is shown in Table 1. The value of mdf=dEdE should be equal to the
number of electrons in CH
4
and the result yields 9.90, as shown in Table 1, only 1% less
than 10. Let us stress from Fig. 2 and Table 1 that the maximum value of df/dE lies
around the ionization potential for the removal of an outer-valence electron and the value
of m
24 eV
11 eV
df=dEdE amounts up to approximately 45% of the total integral. A similar
feature is also seen for a wide range of molecules [1316], and thus let us focus on the
range of the energy of incident photons for the excitation and ionization of valence
electrons as in Fig. 2, i.e., the vacuum ultraviolet range.
We note that the photoionization cross sections (r
i
) of CH
4
is much smaller than the
photoabsorption cross sections (r) just above the rst ionization potential, as seen in Fig. 2.
The values of r
i
then increase as the incident photon energy increases and become almost
equal to those of r around 16 eV. The small dierence between r and r
i
is seen around 22
eV, i.e., just below the (2a
1
)
1
ion state. This feature is shown in a more straightforward
way in the photoionization quantum yields (g
i
) of CH
4
as a function of the incident photon
energy, as seen in Fig. 3 [g
i
=r
i
/r following Eq. (8)]. The signicant deviation of g
i
from
unity around the ionization potentials of the outer-valence electrons is seen for a wide range
of molecules [1316]. This experimental fact of interest is attributed to the excited states of
molecules embedded in their ionization continua. The existence and importance of such
excited states were rst predicted by Platzman in the early 1960s in a pioneering theoretical
work on the interaction of ionizing radiation with matter, and they were named super-
excited states [4,18]. Let us consider a molecule, AB, absorbing a photon of the energy
higher than the rst ionization potential of AB. Then the following processes occur
AB hv !AB
: direct ionization 11
!AB** : superexcitation 12
!AB
: autoionization 13
!AB : neutral dissociation 14
!other processes 15
where AB denotes not only a diatomic molecule but also, more generally, a polyatomic
molecule. The most important feature in the dynamics of a superexcited molecule, AB**, is
the competition between the autoionization [process (13)] and neutral dissociation [process
(14)], because it cannot be seen in a superexcited atom. The processes other than auto-
ionization and neutral dissociation, such as emission of uorescence and ion-pair for-
Table 1 Oscillator-Strength Distribution in CH
4
Energy Range (eV)
Integral of the
Oscillator-Strength Distribution
z23.8 5.15
a
10.9523.8 4.47
b
8.5510.95 0.28
c
Total range 9.90
a
From Ref. [12].
b
From Ref. [7].
c
From Ref. [13].
Source: Ref. [7].
mation, are possible although their contribution is not really signicant. Thus the dierence
between r and r
i
gives the cross section for the neutral dissociation [process (14)] in the
energy range above the rst ionization potential, which is refereed to as the photo-
dissociation cross section in this chapter, r
d
:
r
d
r r
i
16
1 g
i
r 17
The recent stage for the study of the spectroscopy and dynamics of the superexcited
molecules was comprehensively discussed in Ref. [5], and let us stress that the formation of
the superexcited molecules and their decay processes produce a wide range of interesting
structures in the r, r
i
, and r
d
curves as a function of the incident photon energy.
In this chapter, we aim at giving an overview of the photoabsorption (r), photo-
ionization (r
i
d
) cross sections of molecules in the vacuum ultra-
violet range, where as stated the signicant part of the photoabsorption cross sections lies.
2. EXPERIMENTAL METHODS TO MEASURE THE PHOTOABSORPTION,
PHOTOIONIZATION, AND PHOTODISSOCIATION CROSS SECTIONS
2.1. Double Ionization-Chamber Method (Real-Photon Method)
The double ionization-chamber method [19] provides an excellent means of measuring the
photoabsorption cross sections of atoms and molecules in the range of the incident photon
Figure 3 The photoionization quantum yields (g
i
) of CH
4
as a function of the incident photon
energy measured via the double ionization chamber and synchrotron radiation as mentioned in
Section 2.1. The bandpass was 0.1 nm, which corresponds to the energy width of 32 meV at the
incident photon energy of 20 eV. The vertical ionization potentials of the ionic states involved are
indicated by the vertical bars [11] along with the rst adiabatic ionization potential by the arrow [17].
(From Ref. [7]. Reprinted with permission from Elsevier Science.)
energy higher than their rst ionization potentials, and bears several advantages over the
photon-beam attenuation method as follows (see also Fig. 4).
1. The light intensities need not be measured to obtain the photoabsorption cross
sections (r), as will be shown later using Eq. (20). Therefore we do not need to
consider the absorption of light by gas that euses through the entrance and exit
apertures of the chamber.
2. Photoionization quantum yields (g
i
) and, therefore, photoionization cross sec-
tions (r
i
) are obtained together with the photoabsorption cross sections (r).
Fig. 4 shows the illustration of a double ionization chamber. We describe the process
of measuring the photoabsorption cross sections as follows. I
0
denotes the incident photon
ux coming into the chamber lled with atoms or molecules of the number density n, I
1
and I
1
V denote the photon uxes entering and leaving plate 1, respectively, and I
2
and I
2
V
denote the photon uxes entering and leaving plate 2, respectively. The ion currents i
1
and
i
2
collected by plates 1 and 2, respectively, are expressed as
i
1
eg
i
I
0
exprnL
1
1 exprnd 18
i
2
eg
i
I
0
exprnL
2
1 exprnd 19
where L
1
, L
2
, and d are lengths as dened in Fig. 4, and e is the elementary charge. Thus
we obtain
r
ln i
1
=i
2

n L
2
L
1

20
According to Eq. (20), we measure only i
1
, i
2
, and the pressure of a gas in the chamber to
obtain the absolute values of the photoabsorption cross sections (r), and then we obtain
the values of g
i
I
0
from r following Eq. (18) or Eq. (19). If we use a rare gas as reference,
of which g
i
is unity in the whole range above its rst ionization potential, then I
0
is
obtained. Thus the relation between I
0
and the signal from the incident photon detector,
Figure 4 The outline of the double ionization chamber. (From Ref. [19].)
which is not shown in Fig. 4, is determined as a function of the incident photon energy
by using a suitable rare gas as reference. When this relation is known, the quantities i
1
, i
2
,
I
0
, and n are obtained together to give the absolute values of both photoabsorption cross
sections (r) and photoionization quantum yields (g
i
) following Eqs. (1820). From r
and g
i
, the photoionization cross sections (r
i
) and photodissociation cross sections
(r
d
) are easily derived, as mentioned in Section 1: r
i
= g
i
r [Eq. (8)] and r
d
= (1 g
i
)r
[Eq. (17)].
We note that the relation between I
0
and the signal from the incident photon detector
is inuenced by absorption of photons due to gas eusing from the entrance aperture of the
chamber, and thus the ionization chamber needs to be equipped with a suitable window to
prevent gas eusion while measuring the accurate values of g
i
[20,21]. The window is not
needed when aiming to measure only the photoabsorption cross sections (r) as stated
above. However, the use of window is recommended even in measuring r alone, because it
prevents the pressure gradient inside the chamber caused by eusion of gas. It also sup-
presses the contribution from higher-order components that become mixed in the mono-
chromatized photon beam from the continuous-wavelength light source such as
synchrotron radiation.
The important element in the double ionization-chamber method is a photon source
in the vacuum ultraviolet range. Discharge lamps were used in the 1960s and 1970s, and
are still used today. Since 1980s, however, synchrotron radiation has been widely used in
the eld covered by this chapter because of its broadband tunability in the range from the
vacuum ultraviolet radiation to soft X-ray, which is strongly required in measuring the
cross sections as a function of the incident photon energy.
2.2. Fast Electron Impact Dipole-Simulation Method (Virtual-Photon
Method) and Comparison with Real-Photon Method
In electron impact experiments of atoms and molecules for incident electron energies ex-
ceeding 1000 eV, for example, the generalized oscillator-strength distribution, dF(E,K)/dE,
is derived from the electron scattering cross sections dierential with respect to the energy
loss of electrons, E, and the solid angle for scattered electrons according to the BornBethe
approximation, where K is the momentum transfer [3]. The energy loss is equivalent to
excitation energy or photon energy, and thus the symbol E is used to denote the energy
loss as well. The most important characteristics of the generalized oscillator-strength
distribution is [3]:
lim
K!0
dFE; K
dE

df
dE
21
It follows fromthe above discussion that the fast electron scattering experiments at forward
direction is able to simulate the photoabsorption cross sections over a wide range of the
energy loss.
Brion and co-workers [14,2225] have extensively used and applied such an experi-
mental approach by using fast electrons as the virtual-photon source. Brion et al. [14,25]
pointed out some expected characteristics of the use of synchrotron radiation in compar-
ison with virtual photons in studies of the photoionization and photoexcitation of mole-
cules, and claried some necessary assumptions to virtual photons instead of real photons.
It should be noted here, as described below, that these two methods, real- and virtual-
photon experiments, have complementary roles with each other in understanding the
essential features of the interaction of photons with molecules and obtaining the absolute
values of the cross sections (r, r
i
, and r
d
) [7,5,26].
The fast electron scattering (dipole) approach to real-photon experiments using the
virtual-photon source is called the electron impact dipole-simulation method. The dipole
(e, e) method simulates total photoabsorption while coincidence techniques are used for
measurements of the electronic partial photoionization [dipole (e, 2e)] and ionic photofrag-
mentation [dipole (e, e+ion)] cross sections. These virtual-photon experiments are sum-
marized in Table 2 [14] together with the corresponding real-photon experiments. These
simulation experiments have provided a large body of data in comparison with real-photon
experiments of absolute cross sections [14,25]. The real-photon experiments using synchro-
tron radiation, in which a lot of progress in experimental techniques is being made, have
been comprehensively compared with the simulation measurements [5,16], which is briey
described below.
In most cases, except those in earlier comparative studies between the real-photon
method and the dipole-simulation method, the absolute cross-section values obtained by
both methods agree with each other [27]. Comparison of obtained cross-section values be-
tween the two methods were discussed in detail [27, 2, and references therein] and sum-
marized in conclusion [5]. It should be noted, at least briey, that it is essentially dicult to
accurately obtain the absolute values of photoabsorption cross sections (r) in the dipole-
simulation experiments, and it is necessary to use indirect ways in obtaining those values as
the application of the TKR sum rule, Eq. (3), to the relative values of the cross sections
obtained partly with theoretical assumptions. Moreover, in some cases, in relatively earlier
dipole-simulation experiments, particularly of corrosive molecules upon their electron
optics with poorer energy resolutions, serious discrepancy fromthe real-photon experiments
was clearly pointed out in the obtained absolute values of photoabsorption cross sections
[5,20,2528].
As for the absolute values of photoionization quantum yields (g
i
), a situation of the
dipole-simulation experiments in comparison with the real-photon experiments is much
more serious and controversial because their absolute scales are determined by the assump-
tion that the photoionization quantum yields should be unity around 20 eV photon energy
in addition to the above-mentioned diculty in obtaining absolute cross-section values in
the dipole-simulation experiments.
In case of simple diatomic molecules such as H
2
and N
2
, sharp peaks are observed with
large photoabsorption cross sections, especially in the lower energy range. In real-photon
experiments, if the peak shape is narrower in energy than the bandpass of the incident
Table 2 Photon and Electron Impact Experiments
Photon Experiment Equivalent Electron-Impact Experiment
Total photoabsorption Electron-energy-loss spectroscopy, dipole (e, e)
Total photoionization Dipole (e, 2e) or (e, e+ion) (from sums of partials)
Photoelectron spectroscopy Electron energy loss-ejected electron coincidence,
dipole (e, 2e)
Photoionization mass spectrometry Electron-ion coincidence, dipole (e, e+ion)
Source: Ref. [14].
photon beam, the measured photoabsorption cross section suers from the serious line
saturation eect [29]. In such cases, we should refer to the result by the virtual-photon
experiments or the dipole-simulation experiments, because the integrated photoabsorption
cross sections over a range of the incident photon energy for a transition give the correct
value of the oscillator strength of that transition even if the measured shape is aected by
the energy resolution [29,30]. However, it should be noted that the results of the dipole-
simulation experiments are obtained with rather poor energy resolutions, i.e., poorer than
several tens of meV, in comparison with the real-photon experiments, especially in the lower
energy range. It means that some important spectral features in the cross-section curves may
be sometimes missed in the dipole-simulation experiments.
The real-photon method is essentially more direct and easier compared to the dipole-
simulation method in obtaining absolute values of photoabsorption cross sections (r),
photoionization cross sections (r
i
), and photoionization quantum yields (g
i
). In the real-
photon method, however, there is a practical need to use the big and dedicated facilities of
synchrotron radiationwhere, in many cases, one should change the beam lines equipped
with dierent types of monochromators depending on used photon-wavelengthsand to
develop some specic new experimental techniques in the range from the vacuum ultra-
violet radiation to soft X-ray.
In conclusion, as summarized elsewhere [5,26], these two methods have comple-
mentary roles in understanding the interaction of photons with molecules, as well as in
obtaining the absolute values of the cross sections (r, r
i
, and r
d
).
3. PHOTOABSORPTION AND PHOTOIONIZATION OF MOLECULES
OF CHEMICAL INTEREST, NORMAL ALKANESAN OVERVIEW
In this section, we present an overview of the photoabsorption cross section (r) and the
photoionization quantum yields (g
i
) for normal alkanes, C
n
H
2n+2
(n = 14), as a function
of the incident photon energy in the vacuum ultraviolet range, and of the number of
carbon atoms in the alkane molecule, because normal alkanes are typical polyatomic
molecules of chemical interest. In Fig. 5, the vertical ionization potentials of the valence
electrons, which interact with the vacuum ultraviolet photons, in each of these alkane
molecules are indicated to show how the outer- and inner-valence orbitals associated with
carbon 2p and 2s orbitals, respectively, locate in energy [7].
3.1. Photoabsorption Cross Sections of Normal Alkanes
In Fig. 6 [7], the photoabsorption cross sections (r) of CH
4
, C
2
H
6
, C
3
H
8
, and n-C
4
H
10
are
compared, which were measured by our group by using the double ionization chamber
and synchrotron radiation, as described in Section 2.1. Those in the range below the rst
ionization potentials were measured by the photon-beam attenuation method using the
ionization chamber as a conventional gas cell. The following features can be noted [7].
1. Each cross section has a maximum around 1316 eV, and the observed maxima
shift to the higher energies with increasing the number of carbon atoms, i.e.,
from CH
4
to n-C
4
H
10
, while the rst ionization potentials shift to the lower
energies as shown in Fig. 5. This shift of the maxima seems to be amenable to
the trends in the ionization potentials of the deepest outer-valence orbitals of
each molecule.
2. In the energy range below the peak maximum, the r curves show some undu-
lations, which are attributed to either excitation, superexcitation, or ionization
of the outer-valence electrons.
3. Around 1823 eV, vibrational structures are clearly observed for CH
4
, C
2
H
6
,
and C
3
H
8
, which were assigned to the superexcited Rydberg states converging to
the (2a
1
)
1
, (2a
2u
)
1
, and (4a
1
)
1
ion states, respectively. These superexcited
Rydberg states move to lower energies as the number of carbon atoms increases
along the order of the ionization potentials of the 2a
1
electron in CH
4
, 2a
2u
electron in C
2
H
6
, and 4a
1
electron in C
3
H
8
as shown in Fig. 5.
It is dicult to give a simple explanation of the gross features in the r curves in Fig. 6
with existing theoretical knowledge. In this context, it should be noted that Nakatsukasa
and Yabana [31] calculated the absolute values of the photoabsorption cross sections (r)
as a function of the energy of up to 40 eV for SiH
4
(silane), C
2
H
2
(acetylene), and C
2
H
4
(ethylene) based on the time-dependent local density approximation, and obtained good
agreement with the results yielded by real-photon [20,32,33] and virtual-photon experi-
ments [24,28,34]. It is also interesting, in terms of the gross features mentioned above, that
the r curves of cyclic alkanes seem to behave dierently from those of normal alkanes,
e.g., C
3
H
8
(propane) vs. C
3
H
6
(cyclopropane) [35].
Figure 5 Ionization potentials of the valence electrons of CH
4
, C
2
H
6
, C
3
H
8
, and n-C
4
H
10
[8,9,
10,11], which are the vertical ionization potentials of the ionic states produced with the removal of
an electron from each valence orbital. The point groups for the molecules are also shown as well as
the notation of the orbitals based on them. (From Ref. [7]. Reprinted with permission from Elsevier
Science.)
3.2. Photoionization Quantum Yields of Normal Alkanes
In Fig. 7 [7], we compared the photoionization quantum yields (g
i
) of CH
4
, C
2
H
6
, and
C
3
H
8
, which were measured by our group using the double ionization chamber and
synchrotron radiation, as described in Section 2.1. The photon energies are considered in
two ranges, as follows, in terms of the behavior of the g
i
curves as a function of the inci-
dent photon energy [7]:
1. The energy range of the outer-valence electrons, where the g
i
curves rise up
gradually and then reach unity.
2. The energy range of the inner-valence electrons, i.e., higher than approximately
17 eV, where the g
i
curves show small but discernible deviations from unity. The
superexcited Rydberg states mentioned in Section 3.1 play an important role in
these deviations.
The g
i
curves rise up from the rst adiabatic ionization potentials and then reach
unity at photon energies, slightly higher than the ionization potentials of the deepest
outer-valence electrons. The energy dierences between the onsets of the g
i
curves and
the photon energies where the g
i
curves reach unity are approximately 3 eV for CH
4
, 5
eV for C
2
H
6
, and 6 eV for C
3
H
8
, respectively, reecting the dierence between the ion-
ization potentials of the shallowest and deepest outer-valence orbitals shown in Figs. 5
and 7.
Figure 6 The photoabsorption cross sections (r) of CH
4
, C
2
H
6
, C
3
H
8
, and n-C
4
H
10
as a function
of the incident photon energy measured via the double ionization chamber and synchrotron
radiation, as mentioned in Section 2.1. Those in the range below the rst ionization potentials were
measured by the photon-beam attenuation method, using the ionization chamber as a conventional
gas cell. The energy resolution of the incident photon energy at 20 eV is as follows: 32 meV for CH
4
,
29 meV for C
2
H
6
, 29 meV for C
3
H
8
, and 116 meV for n-C
4
H
10
. (From Ref. [7]. Reprinted with
permission from Elsevier Science.)
4. CONCLUSIONS AND FUTURE PROBLEMS
The features in C
1
C
4
normal alkanes discussed in Section 3 seem to be generalized to a
wide range of molecules, and thus we conclude that the major part of the photoabsorption
cross sections of molecules (r) is associated with the ionization and excitation of the outer-
valence electrons. Hence, there is a strong need to measure the absolute values of r in the
vacuum ultraviolet range, particularly in the range of the incident photon energy 1030 eV,
which is covered by the normal incidence monochromator used to monochromatize
synchrotron radiation. The photoionization (r
i
) and photodissociation (r
d
) cross sections,
Figure 7 The photoionization quantum yields (g
i
) of CH
4
, C
2
H
6
, and C
3
H
8
as a function of the
incident photon energy measured via the double ionization chamber and synchrotron radiation as
mentioned in Section 2.1. The energy resolution of the incident photon energy at 20 eV is as follows:
32 meV for CH
4
, 29 meV for C
2
H
6
, and 29 meV for C
3
H
8
. The vertical ionization potentials of the
ionic states involved are indicated by the vertical bars for each molecule [11]. (From Ref. [7].
Reprinted with permission from Elsevier Science.)
which are partial photoabsorption cross sections, are also key quantities for a full under-
standing of the interaction of photons with molecules in the vacuum ultraviolet range. The
structures seen in the cross-section curves as a function of the incident photon energy are
attributed to the superexcited states or shape resonances. In conclusion, the absolute
values of r, r
i
, and r
d
as a function of the incident photon energy in the vacuum
ultraviolet range are quantities to be measured with a foremost priority in investigating
the interaction of photons with molecules from a chemical point of view. However, they
have been measured only for a limited number of molecules [1316]; in particular, the
quantity and quality of the data sets for polyatomic molecules are still insucient. In this
context, we note that it is more dicult to measure the correct and absolute values of r
i
and r
d
than r, because the incident photon ux is needed in measuring the photo-
ionization quantum yields (g
i
) with the double ionization-chamber method, and the
coincidence measurements should be carried out in the dipole-simulation experiments
with the assumption that g
i
is unity around 20 eV photon energy (see also Section 2).
Finally, some future problems that need to be solved from the view point of this
chapter are summarized below.
1. The eect of temperature on the absolute values of r, r
i
, and r
d
as a function of
the incident photon energy. All the cross-section data shown in this chapter were measured
for molecules in the gas phase at room temperature and thus, the target molecules do not
lie in a single energy level as an initial level. This means that the measured cross sections
seem to be dependent on gas temperature, which is important in various applications of
the cross-section data.
2. The measurement of the absolute values of the partial photodissociation cross
sections as a function of the incident photon energy. As mentioned in Section 1, the
interesting structures due to superexcited states appear in the r, r
i
, and r
d
curves as a
function of the incident photon energy. They are much more noticeable in the rd curves
than in the r and r
i
curves because no contribution from ionization is involved in the rd
curves (e.g., see the r, r
i
, and r
d
curves around 22 eV in Fig. 2). It follows that the
measurement of partial photodissociation cross sections provides us with a more
powerful tool to investigate the superexcited molecules than that of r
d
. Most of the
experiments along this idea, however, have yielded just the relative cross sections. We have
recently been successful in measuring the absolute cross sections for the emission of
uorescences by excited CH radicals and hydrogen atoms in the photoexcitation of
methane as a function of the incident photon energy in the range 12.6541 eV, and found
an unexpectedly large contribution from the doubly excited states in terms of the
independent electron model [36]. The dynamics and spectroscopy of doubly excited
molecules are the subject of current interest from the viewpoint of the few-body problem
in quantum mechanics [37], and thus the absolute values of the partial photodissociation
cross sections should be extensively measured.
3. The extension of target molecules from those in the gas phase to the condensed
phase to investigate the eect of density on the cross sections [5]. The extension to clusters
and transient species such as radicals is also important.
ACKNOWLEDGMENTS
The authors wish to thank Drs. Kosei Kameta and Masatoshi Ukai for their eorts in
measuring the absolute values of the cross sections cited in this chapter.
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6
Reactions of Low-Energy Electrons, Ions,
Excited Atoms and Molecules, and Free
Radicals in the Gas Phase as Studied
by Pulse Radiolysis Methods
Masatoshi Ukai
Tokyo University of Agriculture and Technology
Tokyo, Japan
Y. Hatano
Tokyo, Japan
SUMMARY
After a brief survey of recent advances in gas-phase collision dynamics studies using pulse
radiolysis methods, the following two topics in our research programs are presented with
emphasis on the superior advantages of the pulse radiolysis methods over the various
other methods of gas-phase collision dynamics, such as beam methods, swarm methods,
and ow methods. One of the topics is electron attachment to van der Waals (vdW)
molecules. The attachment rates of thermal electrons to O
2
and to other molecules in dense
gases, measured in wide ranges of both gas temperatures and pressures, present exper-
imental evidence for electron attachment to van der Waals molecules. The results are
compared with theories and discussed in terms of the eect of van der Waals interaction
on the electron attachment resonance. The conclusions obtained are related with inves-
tigations of electron attachment, solvation, and localization in the condensed phase.
Another topic is Penning ionization and its related processes. The rate constants for the
de-excitation of He(2
3
S), He(2
1
P), Ne(
3
P
0
), Ne(
3
P
1
), Ne(
3
P
2
), Ar(
1
P
1
), and Ar(
3
P
1
), by
atoms and molecules measured in the temperature range from 100 to 300 K, provide the
collisional energy dependence of the de-excitation cross sections. The results are compared
in detail with theories classied according to the excited rare gas atoms in the metastable
and resonant states, which present a systematic understanding of the de-excitation
processes of excited rare gas atoms. For typical examples, the de-excitation process of
metastable atoms, the de-excitation process of resonant atoms, and the de-excitation
process by molecules containing a group IV element are discussed.
1. INTRODUCTION
Pulse radiolysis is of great importance in the understanding of gas-phase reactions [13].
The results obtained are also useful for understanding condensed phase reactions. The
objectives of pulse radiolysis studies in the gas phase are divided into two parts. One is to
understand the fundamental processes, in particular, early processes in radiolysis. The
other is to make an important contribution, as one of the powerful experimental methods,
to gas-phase collision dynamics studies. Recent advances in the latter studies are surveyed
in this paper; those in the former studies are not included here. The above-mentioned
objectives are, however, closely related with one another in terms of the following interface
relationships. New information obtained from the latter studies is useful for understanding
the fundamental processes in radiolysis, whereas that from the former studies is an
important source of new ideas and information in collision dynamics studies.
Advances in pulse radiolysis studies in the gas phase have been summarized in several
review papers. In a comprehensive review by Sauer [4], a review presented by Firestone and
Dorfman [5] in 1971 was referred to as the rst review on gas-phase pulse radiolysis. Exper-
imental techniques and results obtained were summarized by one of the present authors [6],
with emphasis on an important contribution of pulse radiolysis to gas-phase reaction dy-
namics studies. Examples were chosen by Sauer [7] fromthe literature prior to 1981 to show
the types of species that were investigated in the gas phase using pulse radiolysis technique.
Armstrong [8] reviewed experimental data obtained fromgas-phase pulse radiolysis together
with those from ordinary steady-state radiolysis. Advances in gas-phase pulse radiolysis
studies since 1981 were also briey reviewed by Jonah et al. [9], with emphasis on an impor-
tant contribution of this technique to free radical reaction studies. One of the present authors
reviewed comprehensively the gas-phase collision dynamics studies of low-energy electrons,
ions, excited atoms and molecules, and free radicals by means of pulse radiolysis method
[13]. An important contribution of pulse radiolysis to electron attachment, recombination,
and Penning collision studies was also reviewed in Refs. 1015.
In this chapter, rstly, a very brief survey is given of recent advances in such studies
as classied according to the detection technique of transient species in pulse radiolysis.
Secondly, examples are chosen from our recent investigations, with special emphasis on
the important contributions of pulse radiolysis methods to gas-phase collision dynamics;
one is electron attachment, the other is Penning ionization and related processes. The
detection techniques and corresponding reaction processes, together with major refer-
ences, are given below:
(A) Optical emission and absorption spectroscopy
(1) De-excitation of excited rare gas atoms such as Penning ionization and
related processes (see Section 3)
(2) Formation and reaction of rare gas excimers and exciplexes [1623]
(3) Reaction of atoms and free radicals (see references cited in Jonah et al. [9]).
(4) Electronion or ionion recombination [17,24]
(5) Ionmolecule reaction [25]
(6) Reaction of excited aromatic molecules [26]
(7) Electron thermalization [27]
(B) DC conductivity measurements
(1) Electron mobility [2834]
(2) Electron detachment [35].
(3) Electron attachment (see Section 2)
(4) Electronion or ionion recombination [30,33,36]
(C) Microwave conductivity measurements
(1) Electron attachment (see Section 2)
(2) Electronion or ionion recombination [37]
(3) Electron thermalization [3844]
(4) Penning ionization [45]
(D) Mass spectroscopy
(1) Ionmolecule reaction [4648]
2. ELECTRON ATTACHMENT PROCESSES
Pulse radiolysis, as combined mainly with microwave conductivity techniques, has been
applied to thermal electron attachment studies. The molecules studied are O
2
, N
2
O, NO,
NO
2
, SF
6
, alkyl halides, and peruorocarbons. Alkyl halides, uorocarbons, and N
2
O
were studied in the early 1970s [46,4951], whereas O
2
, N
2
O, and other simple molecules
have been extensively studied with special emphasis on the important contribution of a
pulse radiolysis method to electron attachment studies, in particular, to the studies on
electron attachment to van der Waals molecules [10,11,5270]. In the following, one may
be a unique standpoint of the microwave technique combined with the pulse radiolysis
method in electron attachment experiments. In the study of electron attachment mecha-
nisms, ordinary swarm techniques may have some essential limitations in the experiment
as it is almost unavoidable to use only a few environmental buer gases for which the
swarm parameters, electron energy distributions, etc., are well known. Therefore, in cases
where the attachment mechanism is strongly dependent on the particular nature of the
environmental gases, the technique may not give enough information to adequately
evaluate the mechanism in detail. Usual beam techniques are evidently not suitable for
the study of environmental eects on the attachment mechanism. On the other hand, the
microwave technique has been used as an alternative means for such studies, with the main
advantage of the technique being that it allows us to observe the behavior of thermal
electrons, thus excluding any factor dependent on the electron energy distribution. For
usual swarm and beam techniques, it has been dicult to study electron collision processes
at very low energies such as thermal energy, whereas such studies are obviously of great
importance in the understanding of not only a two-body problem such as electron
interaction with molecules, but also various phenomena in ionized gases. The microwave
technique, combined with the pulse radiolysis method, has shown a distinct advantage in
studying thermal electron attachment to molecules. By employing the pulse radiolysis
method, it is possible to perform a time-resolved observation of decaying electrons with a
very fast response in a very wide range of pressure of an environmental gas, which is
chosen with virtually no limitation. Thus, the mechanism of low-energy electron attach-
ment to molecules has been discussed primarily in terms of the interaction of electrons
with molecules. Recent studies of thermal electron attachment to O
2
, N
2
O, and other
molecules have revealed that the electron attachment to pre-existing van der Waals
molecules or neutral clusters plays a signicant role in the overall mechanism. A signicant
development in such studies has been started in electron attachment studies using
experimental techniques that originated from radiation chemistry; one is the microwave
technique combined with pulse radiolysis (see references cited in Refs. 10 and 11), the
other is the competition kinetics of steady-state g-radiolysis [7173]. Such studies have
made an important contribution to advances in electron attachment studies, as summar-
ized in the last part of this section, and have triggered a very recent development in beam
experiments of electronvdW molecule collisions [7477].
Evidently, the existence of electron attachment to vdW molecules compels us to re-
interpret more or less various experimental data obtained previously. Furthermore, be-
cause such processes must be more important in dense gases or in the condensed phase, the
studies of those processes will provide insight as to the eect of the density on reactions
involving electrons or, generally, on the electronmolecule interaction processes [78].
Because oxygen is probably the most extensively studied molecule in both experimen-
tal and theoretical investigations of low-energy electron attachment, the experimental results
and detailed discussion are presented in this paper particularly for O
2
. The only accepted
mechanism has been the overall two-step three-body mechanism, which was originally
suggested by Bloch and Bradbury [79] (referred to belowas BB) and was later modied by
Herzenberg [80] to make it consistent with modern experimental data. The BB mechanism
for O
2
M mixture, where M is a molecule other than O
2
, is expressed as follows:
e
O
2
!
k
1
O
2
* 1
O
2
* !
k
2
O
2
e
2
O
2
* O
2
!
k
3
O
2
O
2
3
O
2
* M!
k
4
O
2
M 4
The vibrational characteristics of the negative ion O
2
* are established from electron impact

and scattering experiments, and the electron anity of O
2
is 0.44 eV. For convenience, the
potential energy diagrams for O
2
(X
3
R
g
) and O
2
(X
2
P
g
) are shown in Fig. 1. It can be seen
that the lowest resonance involves the vibrational levels, O
2
(v=0) and O
2
(vV=4), at low
electron energies and the resonance energy is about 0.08 eV.
Because all electron decays for O
2
M mixtures in the above-mentioned experimental
conditions show pseudo-rst-order behavior, each decay curve gives an electron lifetime
s
0
, which is related to molecular number densities [O
2
] and [M] as:
s
0
O
2

1
k
1
1
k
M
M 5
when [O
2
]<<[M], where k
M
(=k
1
k
4
/k
2
) is the overall three-body rate constant. Based on
Eq. (5), Shimamori and Fessenden [58] determined the value of k
1
=4.8 10
11
cm
3
/sec and
the value of k
M
for each stabilization partner, which is listed in Table 1 with the value
obtained by other workers. The autoionization lifetime of O
2
* (i.e., the value of 1/k

2
) was
also estimated to be around 10
10
sec, which was comparable to the predictions of some
theoretical treatments [80,9497] (see Table 2).
Some inconsistencies existed between the results obtained by Shimamori and Hatano
[61] and other data. Christophorou [98100], Goans and Christophorou [101], and
McCorkle et al. [102] investigated electron attachment in O
2
C
2
H
4
, O
2
C
2
H
6
, and O
2
N
2
mixtures at very high gas pressures (<30 atm), and observed that the attachment rate in
the O
2
C
2
H
4
system showed saturation at very high pressures, but the rates in O
2
C
2
H
6
and O
2
N
2
mixtures continued to increase steeply with increasing pressures of C
2
H
6
and
N
2
, respectively. They reported the value of k
1
to be much larger than that obtained by
Shimamori and Hatano [61] and, correspondingly, to have a considerably shorter lifetime
of O
2
* (see Table 2). Such inconsistencies have been demonstrated more clearly and
analyzed by the recent work of Kokaku et al. [52,53]. Kokaku et al., in a joint research
between Tokyo and Notre Dame, have studied, using the microwave technique combined
with the pulse radiolysis method, O
2
CO
2
and several O
2
hydrocarbon systems at
pressures from <100 to 1000 Torr and found that the BB mechanism can account for
the data in the low-pressure range but fails to explain the results at higher pressures. The
data for O
2
C
2
H
4
mixtures are shown in Fig. 2 as an example, where the high-density part
of the data agrees well with the data obtained by Goans and Christophorou [101] using a
swarm technique. This research has claried a signicant discrepancy between the values of
k
1
and 1/k
2
obtained by the pulse radiolysis microwave technique and those obtained by the
swarm technique. Thus, it has become obvious that a consistent interpretation in terms of
only the BB mechanism is not possible in a wide range of pressures of M, and additional
mechanisms must be considered to explain the high-pressure data. One of the strong
Figure 1 Potential energy curves for O
2
and O
2
. (From Refs. 10 and 11.)

candidates for such a mechanismis electron attachment to vdWmolecules, as was indicated
by Kokaku et al. [52,53]:
O
2
M,
K
eq
O
2
M 6
e
O
2
M !
k
5
O
2
M
* 7
O
2
M
* !
k
6
O
2
Me
8
O
2
M
* M!
k
7
O
2
M
M 9
Table 1 Three-Body Attachment Rate Constants k
M
for the Reaction e
+O
2
+M!O
2
+M at
Room Temperature (From Refs. 10 and 11.)
M
10
30
(cm
3
/sec) Authors Reference M
10
30
(cm
3
/sec) Authors Reference
He 0.033 Shimamori and Hatano [61] C
2
H
2
1.3 Kokaku et al. [53]
0.03 Chanin et al. [83] 1.5 Christophorou [105]
0.07 van Lind et al. [88] 1.7 Shimamori and Hatano [61]
Ne 0.023 Shimamori and Hatano [61] 0.9 Toriumi and Hatano [68]
Ar 0.05 Shimamori and Hatano [61] C
3
H
8
3.2 Kokaku et al. [52]
Kr 0.05 Shimamori and Hatano [61] 3.3 Shimamori and Hatano [61]
Xe 0.085 Shimamori and Hatano [61] n-C
4
H
10
4.2 Shimamori and Fessenden [58]
H
2
0.48 Shimamori and Hatano [59] 4.5 Kokaku et al. [53]
D
2
0.14 Shimamori and Hatano [59] 5 Shimamori and Hatano [61]
N
2
0.06 Chanin et al. [83] n-C
5
H
12
7.9 Shimamori and Hatano [61]
0.085 Shimamori and Hatano [60] neo-C
5
H
12
7 Kokaku et al. [52]
0.09 Shimamori and Fessenden [58] 8.0 Shimamori and Hatano [61]
0.1 Crompton et al. [84] n-C
6
H
14
0.11 Hegerberg and Crompton [86] C
6
H
6
van Lind et al. [88] 18 Bouby and Abgrall [81]
0.15 Goans and Christophorou [101] CO 1.31 Shimamori and Fessenden [58]
Hackam and Lennon [85] CO
2
3 Bouby and Abgrall [81]
McCorkle et al. [102] Pack and Phelps [90]
0.26 Young et al. [93] Warman et al. [92]
0.10 Toriumi and Hatano [70] Bouby et al. [82]
O
2
1.7 Young et al. [93] 3.2 Kokaku et al. [53]
2.0 Pack and Phelps [90] 3.23 Crompton et al. [84]
2.1 van Lind et al. [88] 3.5 Hegerberg and Crompton [86]
Nelson and Davis [89]
Parlant and Fiquet-Fayard [97]
2.15 Crompton et al. [84]
2.2 Shimamori and Fessenden [54] H
2
O 14 Bouby et al. [82]
Shimamori and Hatano [59] Pack and Phelps [90]
Warman et al. [92] Stockdale et al. [91]
2.3 Hackam and Lennon [85] 15.2 Bouby and Abgrall [81]
Shimamori and Hatano [60] H
2
S 9 Bouby et al. [82]
2.6 Hurst and Bortner [87] 10 Bouby and Abgrall [81]
2.8 Chanin et al. [83] NH
3
6.8 Bouby et al. [82]
2.2 Hegerberg and Crompton [86] 7.5 Bouby and Abgrall [81]
CH
4
C
2
H
4
1.5 Goans and Christophorou [101]
1.7 Bouby and Abgrall [81] CH
3
OH 8.8 Bouby et al. [82]
2.0 Kokaku et al. [52] 9.6 Bouby and Abgrall [81]
2.3 Hurst and Bortner [87] 11 Shimamori and Hatano [61]
2.5 Bouby et al. [82] C
2
H
5
OH 18 Shimamori and Hatano [61]
3 Shimamori and Hatano [61] CH
3
COCH
3
27 Bouby et al. [82]
3.1 Stockdale et al. [91] 35 Bouby and Abgrall [81]
3.4 Stockdale et al. [91]
1.3 Toriumi and Hatano [69]
Table 2 Lifetime of O
2
* (X
2
P
g
, vV=4) (From Refs. 10 and 11)
Lifetimes (10
12
sec) Authors Reference
Theory 300 Herzenberg [80]
170 Koike and Watanabe [96]
72 Koike [94,95]
88 Parlant and Fiquet-Fayard [97]
Experiment 100 Shimamori and Hatano [61]
63 Shimamori and Fessenden [58]
2 Christophorou [98]
Goans and Christophorou [101]
McCorkle et al. [102]
91 Toriumi and Hatano [68]
66 Toriumi and Hatano [70]
Figure 2 Dependence on C
2
H
4
density of the eective two-body rate constant of thermal electron
attachment in O
2
C
2
H
4
mixtures at room temperature. (From Ref. 52.) The dashed curve represents
the expected contribution from the BB mechanism.
where K
eq
is the equilibrium constant for vdW molecule formation. One should note here
that the density of vdW molecules is determined by K
eq
[O
2
][M], and the value of K
eq
can be
estimated by the theoretical treatment of Stogryn and Hirschfelder [103]. Several experi-
ments have provided evidence for the existence of vdW molecules in the gas phase [78,104].
In the kinetic treatment made by Kokaku et al. [52,53], the estimated values of k
5
are (2
20) 10
9
cm
3
/sec depending on M, where it is highly attractive that all the values for k
5
are
much larger than the value of k
1
(=4.8 10
11
cm
3
/sec). This result suggests that in the case
of vdWmolecules, the initial electron capture mechanismdiers substantially fromthe case
of isolated molecules. A recent study by Shimamori and Fessenden [58] has veried clearly
the presence of the vdW mechanism. They have measured the temperature dependence of
three-body rate constants in pure O
2
, O
2
N
2
, and O
2
CO mixtures. The result for O
2
is
shown in Fig. 3. According to the theory of Herzenberg [80], the three-body rate constant,
which corresponds to the experimentally obtained k
M
, can be expressed as:
k
M

2
3
h
2
2pmk
B

3=2
nk
L
1
T

3=2
exp
E
0
k
B
T

10
Figure 3 The temperature dependence of the three-body rate constant of O
2
. (From Ref. 58.) The
broken curve shows the temperature dependence of the rate constant calculated from Herzenbergs
theory. The solid curve shows a calculated rate constant, which involves both the contributions
from the broken curve and the rate constant due to electron attachment to van der Waals molecule
(O
2
)
2
.
where h, m, and k
B
have their usual meanings; k
L
is the Langevins rate constant; n is the
stabilization eciency; T is the absolute temperature; and E
0
is the resonance energy.
Equation (10) predicts a simple decrease in the rate constant with reduced temperature. The
expected curve for O
2
calculated from Eq. (10), assuming n to be unity, is drawn in Fig. 3.
Because an extra contribution that increases with lowered temperature is evident, electron
attachment to the vdW molecule (O
2
)
2
has been proposed to account for this. Similarly, the
importance of electron attachment to (O
2
N
2
) and (O
2
CO) has also been demonstrated.
Because the temperature dependence of k
5
is given by:
k
5

2
3
2ph
2
2pmk
B
3=2
C
5
1
T

3=2
exp
E
r
k
B
T

11
where E
r
and C
5
are, respectively, the energy and the width for the resonance attachment
process (Eq. (7)), both pressure-dependent and temperature-dependent experiments [68
70] have given important rate parameters for the BB mechanism such as the rate constant
for the initial electron attachment to O
2
(k
1
), the lifetime s of O
2
* (i.e., the resonance

width), and the overall three-body attachment rate constants for O
2
C
2
H
6
, O
2
C
2
H
4
, and
O
2
N
2
mixtures. The values of s are again in good agreement with those obtained by
theories (see Table 2). Each three-body rate constant is, respectively, smaller than that
obtained previously, without taking into consideration the vdW mechanism. The value of
k
1
obtained from the O
2
N
2
system [70], which is selected as a convenient system to
determine the value of k
1
, is about 3 10
11
cm
3
/sec. This value agrees within experimental
error with those obtained from the O
2
C
2
H
6
and O
2
C
2
H
4
systems [68,69] and with the
value 4.8 10
11
cm
3
/sec, which was obtained previously by Shimamori and Hatano [61].
This value is also consistent with qualitative results of k
1
obtained by other groups, except
for the value obtained by the extremely high-pressure swarm technique [101]. It should be
noted here that the value 310
11
cm
3
/sec, is in good agreement with the theoretical values
2.510
11
and 2.110
11
cm
3
/sec [9497].
The important rate parameters for the vdW mechanism, such as the rate constant for
the initial electron attachment to (O
2
M), where M = C
2
H
6
, C
2
H
4
, and N
2
, and the lifetime
s of (O
2
M)
* (i.e., the resonance width), have been also obtained from this experiment
and summarized in Table 3 [10]. The value of k
5
in Table 3 is again much larger than the
above-mentioned k
1
values. The resonance energy for e
+(O
2
M)
!(O
2
M)
* is much
smaller than that for e
+O
2
!O
2
*, whereas its width for the former process is much

larger than that for the latter process. The large enhancement in the attachment rate
constant from k
1
to k
5
has been discussed qualitatively as related to the decrease in the
resonance energy and the increase in the resonance width. The reason for the decrease in
the resonance energy has been ascribed to the fact that the resonance state is much
Table 3 Rate Constant k
5
, Resonance Energy E
r
, Resonance Width C
5
, Electron Density v
r
f
r
,
and Cross Section r
h
(From Refs. 10 and 11.)
(O
2
M) E
r
(meV) C
5
(AeV) v
r
f
r
r
h
(A
2
) k
5
(10
11
(cm
3
/sec)
(O
2
N
2
) 20 800 0.71 2500 3000
(O
2
C
2
H
6
) 30 450 0.89 1700 1100
(O
2
C
2
H
4
) 45 270 0.92 1100 380
O
2
88 (E
0
) 10 (C
1
) 0.47 570 3 (k
1
)
stabilized by the polarization interaction between O
2
and M. Such a situation is depicted

in Fig. 4, where schematic potential energy curves are shown for the O
2
M and O
2
M
systems [10,11]. Figure 4 shows that near the equilibrium intermolecular distance, the
eective resonance energy of the O
2
M system is much reduced and even superimposed

on the O
2
M curve. The existence of a number of vibrational states in both ion complex
and neutral systems may be another major factor of the large transition probabilities.
When the resonance width is narrower than the energy distribution of thermal
electrons, the attachment rate constant is expressed as:
k
5

Z
vfrdv v
r
f
r
Z
rdv 12
where v is electron velocity, f is a Maxwellian distribution function of electrons, r is an
attachment cross section, the sux r means a value at resonance energy E
r
. The factor
v
r
f
r
means the density of electrons with velocity v to attach to vdW molecules. The value of
v
r
f
r
is given in Table 3, which shows that v
r
f
r
increases with decreasing resonance energy.
The number of electrons that can attach to vdW molecules increases as compared with
those that can attach to isolated O
2
.
Because the cross section of a resonance process is expressed by the BreitWigner
formula, the energy-integrated cross section is written as follows:
Z
rdv
4p
2
3j
2
C
5
ur
h
C
5
13
where j is the wave number of incident electron, E
r
and C
5
are assumed to be independent
of energy, and r
h
means the eective magnitude of electron attachment cross section,
which equals the geometrical cross section corresponding to the de Broglie wave length for
Figure 4 A model of variation of potential energies for O
2
(v=0)M and O
2
(vV=4)M systems as
a function of intermolecular distance. (From Refs. 10 and 11.)
the incident electron. The values of r
h
are also listed in Table 3. At extremely low-energy
electron collision, such as electron attachment to vdW molecules, a small vdW molecule
is supposed to collide with large electron clouds, of which the cross section is
determined by the size of the de Broglie wave length of incident electrons. With decreasing
resonance energy, therefore, the attachment cross section should increase. It should be
noted that the maximum value of empirically obtained cross-section values for dissociative
attachment processes at low energy is reasonably explained by the de Broglie wavelength
of incident electron [105,106].
The resonance width C
5
is expressed by the Wigners threshold rule. In the case of
isolated O
2
, the resonance state O
2
* (X
2
P
g
, vV = 4) can couple with only one electronic
partial wave with an angular momentuml=2. In the case of vdWmolecules, intermolecular
interaction may couple with additional partial waves such as p-wave and s-wave with low
energy. If a third-body molecule distorts the orbital of O
2
(X
2
P
g
), new attachment
channels can open with lower angular momentum of electrons and the resonance width
may increase.
It has been necessary to make a quantitative calculation of these eects using precise
wave functions of the O
2
M system. Huo et al. [107] made such calculations on the O
2
N
2
system and compared their result with experiments. They were successful in explaining the
large enhancement in the attachment rate constant for vdW molecules using SCF wave
functions corresponding to two geometries, T-shape and linear, for (O
2
N
2
) vdW molecules.
The large enhancement in the attachment rate constant was clearly elucidated quantitatively
in this theoretical calculation by the eect of additional vibrational structures of the vdW
molecule on the attachment process, the symmetry breaking, which allows the molecule to
attach a p-wave electron, and the lowering of resonance energy due to a deeper O
2
N
2
potential in comparison with O
2
N
2
potential, as shown schematically in Fig. 4.
An interesting approach [62,63] to this problem, the use of
18
O
2
instead of
16
O
2
,
further substantiated the electron attachment to vdW molecules. For the BB mechanism,
the isotope eect may be expected to appear as a change in the rates of initial attachment
and autoionization channels, which are caused by a decrease of the resonance energy for
18
O
2
in comparison with
16
O
2
.
As mentioned in the beginning of this section, electron swarm data were reported
[98102] in the O
2
C
2
H
6
, O
2
C
2
H
4
, and O
2
N
2
systems up to about 10
21
molecules/cm
3
(3 10
4
Torr) and simply elucidated only by the BB mechanism. An attempt [52,68,69]
was made, therefore, to elucidate the high-pressure swarm data by the combination of the
BB mechanism and the vdW mechanism. The electron swarm data are well explained up to
about 4 10
20
molecules/cm
3
by the combination of both mechanisms. It is obvious that
the contribution from the vdW molecule is dominant in these density ranges. The large
deviations in the data from the combination of the two mechanisms at densities higher
than 4 10
20
molecules/cm
3
may indicate electron attachment to large vdW molecules
such as O
2
(C
2
H
6
)
2
, or may require additionally some collective properties of these hydro-
carbon molecules to explain the density eect of electron attachment in this region. An
attempt [108,109] was made to explain theoretically such density eects in the whole den-
sity range using the statistical model.
Electron attachment to O
2
has been investigated in supercritical hydrocarbon uids
at densities up to about 10
22
molecules/cm
3
using the pulsed electric conductivity
technique [110], and the results have been explained in terms of the eect of the change
in the electron potential energy and the polarization energy of O
2
in the medium uids. In

general, electron attachment to O
2
is considered to be a convenient probe to explore
electron dynamics in the condensed phase.
A similar conclusion has been obtained also in the case of N
2
O [5458]. It may be
plausible to extract from the results of O
2
and N
2
O systems some general conditions under
which one can predict the existence of electron attachment to vdW molecules [10,11]. The
common feature to both O
2
and N
2
O is that the rate constants of electron attachment to
those isolated molecules are relatively small (10
11
10
13
cm
3
/sec) on an absolute scale. This
is due to the presence of activation energy (i.e., the resonance energy) for electron attach-
ment (0.08 eV for O
2
and 0.23 eV for N
2
O). In contrast, there is virtually no activation
energy in the electron attachment to vdW molecules containing O
2
or N
2
O, thus yielding
much larger rate constants for this process. The formation of vdW complexes appears to
act just like it has an eect of lowering the activation energy or the resonance energy.
Consequently, one may expect to observe the contribution of vdW molecules only for
compounds that have activation energies for electron attachment, or for the molecules of
which attachment cross section for electron energies near thermal energy increases with
increasing electron energy.
One may expect generally that even in the case of molecules with negative electron
anities or with high threshold electron energies for attachment, some environmental
eects or the eect of the vdW molecule formation bring about the large enhancement in
the cross sections or the rate constants for the lower-energy electron attachment to these
molecules. Based on the above discussions, the reasons for this expectation are summa-
rized as follows [10,11]:
(1) The lowering of the resonance energy due to a deeper ion-neutral potential in
comparison with neutralneutral potential of the vdW molecule
(2) The additional vibrational structures of the vdW molecule
(3) The symmetry breaking due to the vdW interaction, which allows the molecule
to attach electron with additional partial waves
(4) The deformation of the molecular structure, or the change of the vibrational
modes due to the surrounding molecules
(5) The eective vibrational relaxation of the formed negative ion with excess ener-
gies due to the presence of a built-in third-body molecule in the vdW molecule.
The distinct features of the electron attachment to vdW molecules as summarized
above may become a substantial clue to understand the fundamental nature of electron
attachment not only in dense gases but also in the condensed phase [10,11]. It is also
apparent that most of the electron attachment processes in the bulk system are no longer a
simple process, as in the interaction of electron with isolated molecules. A denitely
important role of pre-existing vdW molecules formed by weak intermolecular forces must
be admitted. From this point of view, interesting phenomena in ionized gases, such as the
attachment cooling eect [111115] and the response time of the air-lled fast-response
ionization chamber (J. W. Boag, 1984, private communication; R. W. Fessenden, 1985,
private communication), should be analyzed by taking into account the important role of
vdW molecules in the electron attachment mechanism.
Another recent aspect of the research of electron attachment processes, using the
pulse radiolysis method combined with the microwave cavity technique, has been
presented by a further combination of microwave electron heating [116]. This new
technique has enabled to measure the electron attachment rate constants as a function
of the mean electron energy in the range of 0.0051 eV (Fig. 5). The new measurements
have been made for various molecules, such as c-C
7
H
14
, CH
3
I, and CH
2
Br
2
[116,117],
which have clearly revealed the disadvantage of the pseudo-free electron attachment by the
collisional electron transfer using the higher-lying Rydberg atoms [117], which was
assumed to be reliable for electron attachment in subthermal region. The pulse radiolysis
microwave cavity technique, combined with microwave heating, has been further com-
bined with the analytical unfolding technique by Shimamori et al. [118], which has made
it possible to derive the attachment cross sections as a function of electron energy (i.e., the
attachment cross sections in the region between the subthermal and subexcitation electron
energy are continuously determined within the same experiment). The extremely low-
energy electron attachment processes have been uncovered for the target molecules of
C
6
F
5
X (X = F, Cl, Br, and I) [118], C
6
H
5
X (X = Cl, Br, and I) [119], various brominated
ethanes and ethylenes [120], brominated methanes [121], and CHCl
3
[122]. The informa-
tion of electron collision processes at such extremely low energies is not available by the
resonant electron scattering method because of experimental diculties. The new pulse
radiolysis method will certainly provide the qualitatively brand-new information on the
thermal electron attachment.
3. DE-EXCITATION OF EXCITED RARE GAS ATOMS
De-excitation processes of excited rare gas atoms in the lowest excited states have an
important role in various phenomena in ionized gases. Recently, the importance has
Figure 5 Left panel: Rate constants k for electron attachment to C
6
F
6
as a function of the mean
collisional energy. (From Ref. 118.) (o) The results obtained using the pulse radiolysis microwave
cavity technique combined with microwave electron heating; (
.
) previous results by Shimamori et al.
[J. Chem. Phys. 1993, 99, 7789]; (
z
) electron swarm [Spyrous and Christophorou, J. Chem. Phys.
1985, 82, 1048]; and (w ) high-Rydberg atom beams [Marawar et al., J. Chem. Phys. 1988, 88, 2853].
Right panel: Comparison of the cross section r(e) for attachment to C
6
F
6
as a function of the
electron energy, () derived by unfolding the rate constants (From Ref. 118.) with the previous cross
sections; ( ) Chutijan and Alajajian [J. Phys. B 1985, 18, 4159]; () Datkos et al. [J. Chem.
Phys. 1993, 98, 7875]; and (o) Grant and Christophrou [J. Chem. Phys. 1976, 65, 2977].
further been recognized in the control and modeling of reactive plasmas in industrial
applications [123].
These atoms are produced both in the primary excitation processes in the radiation
interaction with gases and in the electronion recombination followed by the collisional
and optical relaxation processes. Penning ionization by long-lived metastable atoms has
been studied experimentally using W-value methods, static afterglow methods, owing
afterglow methods, beam methods, and pulse radiolysis methods [1,2,10,124]. Compara-
tive discussions on the methods concluded a superior advantage of the pulse radiolysis
method [1,2], which was best demonstrated by Ueno and Hatano [125], over the other
methods in determining absolute rate constant or cross-section values for this process. A
further advantage of the pulse radiolysis method was presented for obtaining the absolute
values of the rate constants or cross sections for short-lived excited rare gas atoms in
optically allowed or resonant states by Hatano [2] and by Ukai and Hatano [12].
3.1. De-excitation of Excited Rare Gas Atoms in Metastable States
The main de-excitation processes for He(2
3
S) atoms are considered to be Penning
ionization (Eq. (14)) or associative ionization (Eq. (15)):
He2
3
S M!He M
14
He2
3
S M!HeM
15
The ionizing reaction occudrs over a certain range of intermolecular distance R, where
He(2
3
S) and M can be regarded as intermediate quasi-molecules.
According to the theoretical investigations by Nakamura [126128] and Miller [129],
the collisional energy dependence of these processes can be calculated if the interaction
potential V(R) for the system He(2
3
S)M and the autoionization rate C(R)/h from the
intermediate quasi-molecule [He(2
3
S)M] to the resulting quasi-molecular ion [HeM]
+
e
are known. For example, by the classical formula of Miller [129], we have theoretical cross
sections for Penning ionization as:
rE 2p
Z
l
0
b 1 exp 2
Z
l
R
0
CR
t
dR
v

db 16
where R
0
is the classical turning point, v is the relative velocity, and l is the reduced mass.
The interaction potentials and the autoionization widths have been obtained in atomic
scattering experiments only for some simple target molecules, such as rare gas atoms and
hydrogen molecules. The proposed mechanism of autoionization via electron exchange is:
He2
3
S1 M2 !He2 M
1
He2
3
S1 M2 !He2M
1
where (1) and (2) denote the excited electron of the metastable He atom and the electron of
M, respectively. The empirical forms of V(R) and C(R) commonly employed as the most
reliable for theoretical analyses [130133] are:
CR A expaR 17
V*R B expbR 18
where A, B, a, and b are constants and R is an intermolecular distance.
The de-excitation rate constants of He(2
3
S) and Ne(
3
P
0
,
3
P
1
, and
3
P
2
) by various
atoms and molecules were obtained at room temperature using a pulse radiolysis method
[125,134136].
Experimental details for the cross-section measurements were presented in the
literature. Briey, after the irradiation by electron beam pulse for a few nanoseconds,
the time-dependent absorption for the atomic line transition Rg**!Rg*+hv was
measured to observe the time-dependent population of the excited rare gas atoms Rg*.
The population of excited Rg* was determined using an absorption law for the atomic
lines, where the broadening of the absorption prole due to the thermal Doppler eect and
due to the attractive interatomic potentials was reasonably taken into consideration. The
time-dependent optical emission from energy transfer products, such as:
He2
3
S N
2
!He1
1
S N
2
B
2
R
g

;
N
2
B
2
R
g

!N
2
X
2
R
g

hv
was also measured to monitor the population of Rg* [125,126].
An attempt has been made to correlate the rate constant values obtained with vari-
ous molecular parameters such as ionization potentials and polarizabilities. A relatively
good correlation has been obtained for He(2
3
S) [134], as shown in Table 4 between the de-
excitation probability P (=k
M
/k
C
) and the excess energy DE [=E(He
*
) IP
M
], where k
M
,
k
C
, E(He*), and IP
M
are the experimentally obtained rate constant, the calculated gas
kinetic rate constant, the excitation energy of He(2
3
S), and the ionization potential of the
target atom or molecule M, respectively. However, the reason for the correlation has not
been well understood. A similar experiment was made [135,136] also for the de-excitation
of Ne(
3
P
0
,
3
P
1
, and
3
P
2
) by atoms and molecules. Two new features of the obtained results
have been demonstrated in this experiment: one is the J-dependent de-excitation cross sec-
tions, the other is a comparison between a theory of the de-excitation of optically allowed
resonant state and the experimental result of Ne(
3
P
1
), which is partly allowed because of
a weak spinorbit coupling. A pulse radiolysis is very advantageous to obtain not only
absolute de-excitation rate constants or cross sections but also their collisional energy
dependence. Avelocity-averaged absolute cross section r
M
is obtained as a function of mean
collisional energy E from the temperature dependence of an absolute rate constant. The
temperature dependence of the rate constants for the de-excitation of He(2
3
S) by atoms and
molecules has been measured [122] in the temperature range from 133 to 300 K (Fig. 6).
From the above classical formula of the Penning ionization cross section, the collisional
Table 4 Derived Parameters for De-excitation of He(2
3
S) (From Ref. 137.)
M a/b P DE (eV)
IPM=IPHe2
3
S
p
N
2
1.4 0.05 4.24 1.81
CO 1.1 0.07 5.81 1.71
Ar 1.0 0.07 4.06 1.82
Kr 1.0 0.07 5.82 1.71
NO 0.6 0.16 10.56 1.39
O
2
0.6 0.18 7.75 1.59
C
2
H
4
0.3 0.31 9.31 1.48
CO
2
0.1 0.39 6.04 1.70
energy dependence of its cross section is readily given, if the interaction potential V*(R) for
He(2
3
S)M and the autoionization rate C(R)/ t from He(2
3
S)M to He(M
+
e
) are
obtained, by the following simple equation:
r
T
/ E
a=b1=2
or kT / T
a=b
19
where r
T
and k(T) are the total Penning ionization cross section and the corresponding
rate constant, respectively. The slope of loglog plots of k(T) vs. T gives the values of a/b
(Fig. 7) [137]. The obtained a/b value for each molecule M listed in Table 4 increases with
decreasing value of P, where P is a de-excitation probability per collision, or 1/P is an
eective collision number for energy transfer. Because Pis not so relatively dierent for each
M, Table 4 shows clearly that the bigger a (i.e., the shorter range interaction between
He(2
3
S) and M) gives the smaller P(i.e., the less ecient energy transfer fromHe(2
3
S) to M).
This conclusion satises the exterior electron density model by Ohno et al. [138].
3.2. De-excitation of Excited Rare Gas Atoms in Resonant States
De-excitation of the excited rare gas atoms in the resonant states has been studied less
extensively than that of the metastable atoms. This is due to experimental diculties
caused by the short lifetimes of the resonant atoms. There have been reported, however,
several theoretical formulations [139,140] based on a long-range dipoledipole interaction
Figure 6 Collisional energy dependence of the cross sections for de-excitation of He(2
3
S) by (n)
N
2
; (O) Ar; (
y
) CO; ( w ) Kr (left panel); (D) O
2
; (z) NO; (.) C
2
H
4
; and (o) CO
2
(right panel).
(From Ref. 137.)
for the de-excitation cross section of radiative atoms. It is, therefore, necessary to compare
the theory with the results of the resonant or the lowest radiative state atoms. It was re-
ported [141,142] that the collisional energy dependence of the de-excitation cross sections
of He(2
1
P), Ne(
3
P
1
), Ar(
1
P
1
), and Ar(
3
P
1
) by atoms and molecules, using a pulse radiolysis
method, is very advantageous to obtain the absolute values of the de-excitation cross sec-
tions of the resonant atoms as well as the metastable atoms. The experimental technique
of the time-dependent optical atomic line absorption is almost the same as that for the
metastable states.
A comparison, as shown in Fig. 8, between the experimental results of the collisional
energy dependence of the de-excitation cross section of He(2
1
P) by Ar and the theoretical
ones calculated from the WK theory [140] and the KW theory [139] makes clearly
possible for the rst time to compare in detail the experimental results with the theoretical
ones [141]. Previous comparisons between experiments and theories have been made only
for a value of the rate constant or the cross section, respectively, at a particular temper-
ature of collisional energy, usually at room temperature. The results of temperature-
Figure 7 Loglog plot of k
M
for He(2
3
S) vs. T. (From Ref. 137.) The same symbol indicates the
same quenching gas as in Fig. 6.
dependent measurement using the pulse radiolysis method supports evidently the modied
new theory, the KW theory [139], which means that the theory should take the bent tra-
jectory into consideration.
A classical expression for the cross section for collisional de-excitation of He(2
1
P) is
also derived from the formula by Eq. (16). However, the autoionization widths C(R) for
Penning ionization by resonant atoms are not identical to the empirical form of Eq. (18)
for electron exchange. Instead, a direct transition due to a dipoledipole interaction is
proposed to govern this Penning ionization [126,139,140,143], that is,
He2
1
P1 M2 !He1 M
2
He2
1
P1 M2 !He1M
2:
Figure 8 Experimental de-excitation cross sections of He(2
1
P) by Ar, Kr, and Xe (denoted by
circles). (From Ref. 144.) (), ( ), and ( ) represent r
WK
for Ar, Kr, and Xe. The ()
curve shows r
KW
for Ar.
According to the dipoledipole interaction, C(R) is given by the equation:
CR
2pl
2
He
l
2
M
R
6
1 3cos
2
h 20
where l
2
He
and l
2
M
are squared matrix elements for transitions of He! He(2
1
P) and
M!M
+
+e
at 58.4 nm, respectively; h is the angle between the intermolecular axis and
the direction of the atomic 2p polarization. The values of l
2
He
and l
2
M
are obtained from
optical oscillator strengths for He and the relevant atoms and molecules. Using Eq. (20)
together with an appropriate treatment for the p-state polarization during a collision,
Watanabe and Katsuura [140] (WK) proposed a formula of the Penning ionization cross
section as:
r
WK
13:88
l
2
He
l
2
M
tv

2=5
21
In the WK theory, the direction of the polarization axis of He(2
1
P) is carefully con-
sidered, but only rectilinear trajectories for relative motion are considered. The assumption
of the rectilinear trajectories has been generally employed in the theories for higher-energy
heavy- particle collisions, where the forward scattering is dominant. However, because the
relative collisional energy is comparable to the depth energy of the interaction potential well
in the thermal collisions, the assumption of the rectilinear trajectories can give rise to a
considerable disagreement with experimental cross sections, which will be discussed in this
section. The maximum limit for the cross section has been obtained by Katsuura [143] also
by assuming linear trajectories together with the perturbed rotating atom approximation
(i.e., the atomic polarization of He(2
1
P) is directed toward M throughout a collision).
The cross-section measurements using the pulse radiolysis method provided the
opportunity to examine the applicability and inapplicability of the WK theory systemati-
cally. Fig. 8 shows the experimental de-excitation cross sections of He(2
1
P) by Ar, Kr, and
Xe [144]. The values of the cross sections are, on the whole, extremely large in comparison
with simple energy transfer cross sections between neutral atoms and molecules, and
closely approach gas-kinetic close collision cross sections [125,134]. As compared with the
results in Section 3.1, the cross sections are more than one order of magnitude larger than
those for the metastable atoms. The cross section for Xe is larger than that for Kr in the
present energy region, whereas the cross section for Ar is smaller than that for Kr.
The cross sections show a decrease with increasing collisional energy, which is in
marked contrast to the de-excitation cross sections of He(2
3
S) atoms by the same
quenching atoms, as presented in Fig. 6. However, this behavior is rather similar to other
quenching molecules, such as CO
2
and C
2
H
4
, where the cross sections are fairly large, on
the order of tens of squared angstroms.
Relatively good agreement between the experimental and theoretical cross sections is
obtained for the absolute values and also for the collisional energy dependence of the cross
sections. In detail, the experimental values for Kr and Xe are larger than r
WK
and the
dierence increases at lower energies. On the other hand, the experimental cross section for
Ar is smaller than r
WK
and the dierence increases at higher energies. It is known that the
values of l
M
2
are almost the same for Ar, Kr, and Xe, but the value for Xe is a little smaller
than those for Ar and Kr, so that the cross-section values should be in the order of
r
Xe
<r
Ar
<r
Kr
(see r
WK
in Fig. 8). However, the experimental values are r
Ar
<r
Kr
<r
Xe
.
The dierences between r
Ar
and r
Kr
and between r
Kr
and r
Xe
are much greater than those
calculated fromEq. (21). Thus, the absolute values, the order, and the energy dependence of
the experimental cross sections are found to be dierent from those predicted by r
WK
. A
similar consideration was also made for molecular target in He(2
1
P)H
2
collision [145].
To make the comparison a little more obvious, Fig. 9 shows the cross-section ratios
of the experimental values of r
M
to r
WK
plotted against the collisional energy. The ratio
for Xe is larger than unity and decreases with increasing collisional energy. The value for
Kr is also larger but decreases almost to unity with increasing energy. The ratio for Ar is
smaller than unity and continues to decrease with increase in energy, a result that is in
good agreement with a classical trajectory calculation by Kohmoto and Watanabe [139]
(r
KW
). The ratios presented in Fig. 9 suggest that the inuence of the classical motion of
the colliding particles is important in determining the absolute cross sections.
Fig. 10 shows the relation between the experimental values r
M
and the theoretical
predictions r
KW
, together with the experimental cross sections previously reported for the
de-excitation of He(3
1
P) [146,147]. The dierence between the values for He(2
1
P) and
He(3
1
P) is explained by the dierence in the optical oscillator strengths for the two states.
The experimental values can generally be explained by r
WK
based on the long-range
Figure 9 Ratios of experimental cross section to WK cross section for de-excitation of He(2
1
P) by
Ar, Kr, and Xe (circles). (From Ref. 144.) () represents the ratio of r
KW
/r
WK
for Ar.
dipoledipole interaction. However, each of the cross sections is characteristically dier-
ent from the theory, which seems to be much beyond any possible systematic error.
The value of r
M
for Ar is smaller than the theory, but for CO
2
, SF
6
, or NO, r
M
exceeds r
WK
. The positive dierence for diatomic molecules other than H
2
and D
2
is more
than that for rare gas atoms, which is also observed for He(3
1
P).
The result for He(2
1
P)Ar in Fig. 9 shows that the long-range attractive part of
the interaction potentials has a close relation with the polarizabilities of the molecules, M.
Fig. 11 is a plot of r
M
/r
WK
vs. a
M
, the polarizability of M. As for Ar, Kr, Xe, CH
4
, and
SF
6
, some correlation is observed. From the slope of the r
M
/r
WK
vs. a
M
plots, the eect of
bent trajectories on the Penning ionization cross sections can be qualitatively evaluated
Figure 10 Comparison of r
M
for He(2
1
P) to r
WK
(From Ref. 144.): (o) present results; (.) cross
section for He(3
1
P) at 300 K (From Ref. 146.); and (E) cross section for He(3
1
P) at 600 K. (From
Ref. 147.)
because, for molecules with large polarizabilities, the attractive potential extends to large
intermolecular distances, whereas for molecules with smaller polarizabilities, the potential
becomes repulsive sooner at relatively smaller intermolecular distances. On the other hand,
for CO
2
and diatomic molecules, there is no same correlation between the cross-section
ratios and the polarizabilities observed for the rare gas atoms and spherical molecules,
although some other correlations characteristic of these molecules might be distinguished.
The eect of bent trajectories due to the attractive interaction on the absolute cross
section is further claried by the classical trajectory calculation shown in Fig. 12. The cross
section was calculated for He(2
1
P)Ar, He(2
1
P)Kr, and He(2
1
P)Xe collisions assuming
h=0 (perturbed rotating atom approximation [143]) in Eq. (20) for the autoionization
widths, employing the interaction potentials determined in cross-beams experiments for
He(2
1
S)M collisions, and using Eqs. (14)(16) for the general procedure [144]. The cal-
culated cross sections in general are strongly dependent on the collisional energy. However,
Figure 11 Cross section ratios of He(2
1
P) vs. a
M
. (From Ref. 142.) The horizontal lines show the
limits of a
M
values if seen in parallel or perpendicular direction to the molecular axis.
the energy dependence is dierent in each case, thus changing the relative order of the
absolute magnitudes.
The order in the high-energy region is, as expected from the rectilinear calculations
[125,128], r
Xe
<r
Ar
<r
Kr
. However, below 50 meV, the calculation reproduces the experi-
mental order of r
Ar
<r
Kr
<r
Xe
. The result demonstrates that the eect of entangled
trajectories decreases with the increase in the collisional energy. The behavior of the
experimental cross sections has been further examined by a classical trajectory calculation
employing the procedure of KW [139]. The problem of whether the direction of the polar-
ization axis of He(2
1
P) is conserved or not during a collision has also been examined. For Ar,
an atomic target of small polarizability, the experimental cross section is in good agreement
with the KW-type calculation for a spatially xed orientation. For Xe, which has a large
atomic polarizability, r
M
is more closely predicted by the perturbed rotating atom
Figure 12 Calculated Penning ionization cross sections for collisions: ( ) He(2
1
P)Ar, (),
He(2
1
P)Kr, and () He(2
1
P)Xe, assuming classical trajectories for relative motion. (From
Ref. 144.) A perturbed rotating atom approximation is employed in the evaluation of the magnitudes
of the dipoledipole interaction (h = 0; see Eq. (20)). Theoretical values by Katsuura at 500 meV
employing rectilinear trajectories are also indicated. (From Ref. 143.)
approximation. Therefore, in addition to the bent trajectories, the rotation of the polar-
ization axis is also probably an important factor in determining the absolute magnitude of
the cross sections. This includes an important collision physics, namely the angular
momentum of polarized He(2
1
P) during a collision, which should be quantized relative to
the interatomic axis or should remain in the initial xed space.
As for a total decay width of the transient autoionizing state of [HeM]* formed
during a collision, the direct transition due to the dipoledipole interaction and the tran-
sition with the electron exchange should also be involved simultaneously. Because the
outermost electron orbitals of the target rare gas atoms, CH
4
and SF
6
, are fully occupied,
the electron density outside their van der Waals sphere is supposed to be quite low. How-
ever, most of the linear molecules considered here have some amount of electron density
outside their hard sphere, so that the contribution from a short-range interaction (i.e.,
electron exchange), which is neglected in WK, might also be included in the total de-
excitation cross section.
In the present discussion, the total autoionization width for Penning ionization of
He*M or for decay of the transient molecular autoionizing state of [HeM]* is assumed to
be divided into two components: a dipoledipole part and an electron exchange part. The
maximum width possible is assumed to be the sum of the two components [142], that is,
C
total
C
dd
C
ex
22
where C
total
is the total decay width of [HeM]*, and C
dd
and C
ex
are the partial widths due
to the dipoledipole interaction and the electron exchange interaction, respectively.
Substitution of Eq. (22) into the classical formulation of the Penning ionization cross
section, as shown by Eq. (16), gives the theoretical cross section for simultaneous
contributions from both the dipoledipole interaction and the electron exchange.
First, in cases where the transition (ionization) rate is small, the total cross section
will be given by:
r
total
r
dd
r
ex
23
where r
dd
and r
ex
are the components of the cross section due to the dipoledipole inter-
action and the electron exchange interaction, respectively. Fig. 13 gives plots of (r
M
r
WK
)
vs. r
m
, the de-excitation cross section of the metastable helium atoms.
The values of r
m
are assumed to represent the exchange part of the total de-excitation
cross section for He(2
1
P). The values of (r
M
r
WK
) are a measure of the cross section due
to interactions other than the dipoledipole interaction (i.e., the electron exchange inter-
action). The plots in Fig. 13 are shown for linear molecules and also for Xe, CH
4
, and SF
6
.
The values of (r
M
r
WK
) for Ar and Kr are negative and are not included in the gure.
A good correlation is found for H
2
, D
2
, N
2
, CO, O
2
, and CO
2
. A better, or rather more
proportional, correlation is obtained for r(2
1
S) than for r(2
3
S), demonstrating the con-
tribution from the electron exchange. The large deviation observed for NO is explained
by the inapplicability of the WKtheory for transitions other than sp (rp) type. Xenon and
SF
6
also seem to be within the correlation and may have a minor contribution from the
electron exchange interaction.
Secondly, the cross section reects the nature of the dependence of the partial widths
on the intermolecular distance R. As expected from Eq. (20), C
dd
is small for large R and
increases gradually with decrease in R. On the other hand, C
ex
in its empirical form (Eq.
(17)) is extremely small at large distances and increases sharply near the repulsive wall.
Therefore, the de-excitation probability due to Penning ionization is determined by the
dipoledipole part of the decay width in collisions with large impact parameter, whereas
the probability for Penning ionization is already almost unity by the single contribution
from the dipoledipole part in collisions with a small impact parameter where the
trajectory intersects the intermolecular region in which C
ex
is comparably large relative
to C
dd
. The reason why the cross sections for a rare gas target can be explained almost
completely by the dipoledipole interaction originates from this relationship. As expected
from the results for metastable atoms in Table 4, the molecules CO
2
, O
2
, and NO could
have large C
ex
at relatively large R, and the cross sections may have contributions from the
exchange part even at large R, additional to the dipoledipole part.
The above conclusion based on the cross-section measurements, using the pulse
radiolysis method and with consideration of the Penning ionization mechanism including
the classical trajectory analysis, is further rationalized by a quantum mechanical calcu-
lation for He(2
1
P)Ar, Kr, Xe, H
2
, and N
2
collisions [148,149], where the radial wave
function for relative motion is numerically solved by taking into account the partial widths
for dipoledipole interaction and electron exchange interaction. Fitting the calculated
Penning ionization cross sections to the experimental cross sections enables to determine
the interaction potentials for these collision systems for the rst time (Fig. 14), which was
not obtained by the scattering experiments. This is also recognized as an advantage of the
pulse radiolysis method, which provides the insight of intermolecular interaction.
Figure 13 Plots of (r
M
r
WK
) vs. r
m
for an analysis of the de-excitation cross section r
M
for
He(2
1
P), where the de-excitation cross section r
m
for the metastable helium atoms is assumed to
represent the exchange part of the total de-excitation cross section. (From Ref. 142.) The r
m
values
are for He(2
3
S) (o) and He (2
1
S) (.).
It is also a fact that very few studies have been reported on simple excitation transfer,
in which Penning ionization is energetically impossible, from resonant rare gas atoms
to atoms and molecules. The temperature dependence of the de-excitation rate constants
of the resonant states of Ar,
1
P
1
, and
3
P
1
by SF
6
and N
2
has been measured in the tem-
perature range from 133 to 300 K using a pulse radiolysis method [150], thus obtaining
the collisional energy dependence of the de-excitation cross sections. The results of the
cross sections for SF
6
are compared with the WK theory and a good agreement is ob-
tained. The results for N
2
agree with predictions of the cross sections for a nonresonant
case. Even in the case of the de-excitation of the resonant state, such as Ar(
1
P
1
) or Ar(
3
P
1
),
the cross-section value and its collisional energy dependence are very similar to those for
the metastable state (i.e., Ar(
3
P
0
) or Ar(
3
P
2
)). This result is consistent with the WK theory
because of the fact that N
2
has almost no optical absorption in the energy region
Figure 14 Interaction potential and autoionization decay width employed and determined in the
calculations for He(2
1
P)M; ( ) M=Ar; ( ) M=Kr; and () M=Xe; (a) interaction
potential: position of the repulsive potentials for He(2
1
P)Kr and He(2
1
P)Xe are determined by
tting to the experimental results; (b) autoionization decay width for Penning ionization.
corresponding to the excitation energy of Ar(
1
P
1
) and Ar(
3
P
1
). It is concluded, therefore,
that a long-range dipoledipole interaction is important in the de-excitation processes of
Ar(
1
P
1
) and Ar(
3
P
1
) by SF
6
, but that a short-range interaction with curve crossing
dominates in the de-excitation of Ar(
1
P
1
) and Ar(
3
P
1
) by N
2
.
A little more complicated system is the de-excitation of He(2
1
P) by Ne, where the de-
excitation is dominated by the excitation transfer and only a minor contribution from the
Penning ionization is involved. The experimental cross section obtained by the pulse
radiolysis method, together with the numerical calculation for the coupled-channel radial
Schro dinger equation, has clearly provided the major contribution of the following
excitation transfer processes to the absolute de-excitation cross sections [151] (Fig. 15):
He2
1
P Ne !He Ne*6p
3
; 5s
2
; and6s
4
:
3.3. De-excitation of Excited Rare Gas Atoms by Molecules Containing
a Group IV Element
De-excitation cross sections of He(2
3
S, 2
1
S, and 2
1
P), Ne(
3
P
2
,
3
P
1
, and
3
P
0
), and Ar(
3
P
2
,
3
P
1
,
3
P
0
, and
1
P
1
) by molecules containing group IV elements were obtained by the pulse
Figure 15 Calculated total and state-to-state excitation transfer cross sections in the de-excitation
of He(2
1
P)Ne. (From Ref. 151.) Both electron exchange and dipoledipole interactions are included
in the coupling matrix elements. The threshold energy into each exit channel is shown on the upper
axis.
radiolysis method [152155]. The study was designed from the viewpoint of the control of
reactive plasmas. As can be seen in the above, in reactive plasmas, the excited rare gas
atoms in dierent excited states are produced simultaneously and react with atoms and
molecules with dierent probabilities. Thus, the cross-section data for dierent excited
atoms are strongly required.
Table 5 presents the de-excitation cross sections for dierent excited helium atoms.
As demonstrated in the preceding sections, the de-excitation cross sections of He(2
3
S) and
He(2
1
P) are the Penning ionization cross sections. It is natural that these cross sections are
also understood as the Penning ionization cross sections. In general, the cross sections are
extremely large compared with a simple energy transfer cross section between a neutral
atom and a neutral molecule, and they approach the gas-kinetic collision cross sections.
The values in Table 5 show an apparent dependence on the particular excited states of the
helium atoms (i.e., the cross sections for the metastable atoms, He(2
3
S) and He(2
1
S), are
much smaller than those for the resonant atom, He(2
1
P), whereas the cross sections for
He(2
1
S) are larger than those for He(2
3
S)). The behavior of the de-excitation cross
sections, dependent both on the helium excited states and the target molecules, is ascribed
to that of the Penning ionization cross sections. A systematic comparison in Table 6
between the total de-excitation cross sections and the partial cross sections for possible
fragmentation conrms that the Penning ionization is the major de-excitation mechanism.
For example, the optical emission cross sections in a UVvisible region from Si* atoms in
several excited electronic states produced in He(2
3
S)SiH
4
collisions are reported to be
0.081 A
2
. Minor emission from other excited fragments H*, SiH*, SiH
2
*
, and SiH
3
*
does
not increase the cross section signicantly. The production of nonemitting fragments H,
Si, SiH, SiH
2
, and SiH
3
has been shown to give a minor contribution of such fragments to
the formation of neutral products. The cross section of 0.081 A
2
thus represents the total
cross section for the production of emitting neutral fragments, or possibly the total cross
section for the neutral dissociation of SiH
4
in He(2
3
S)SiH
4
collisions. The de-excitation
cross section of He(2
3
S) by SiH
4
in Table 5 is, however, determined to be 18 A
2
in the present
experimenta value that is more than about 200 times larger than that of the optical
emission cross section. It is, therefore, concluded that a major part of the de-excitation
processes in He(2
3
S)SiH
4
collisions is due to processes other than the formation of neutral
dissociation fragments (i.e., due to Penning ionization). The Penning ionization here then
Table 5 De-excitation Cross Sections (r
M
) at a Mean Collisional Energy Corresponding to
Room Temperature (295 K) and De-excitation Probabilities ( P) of Excited Helium Atoms He
*
(He
*
=He(2
3
S), He(2
1
S), and He(2
1
P)) and polarizabilities (a
M
) of target molecules (From Ref. 154.)
M
2
3
S 2
1
S 2
1
P
a
M
(A
3
) r
M
(A
2
) P r
M
(A
2
) P r
M
(A
2
) P
CH
4
14 F 1 0.127 58 F 3 0.461 98 F 9 0.792 2.59
SiH
4
18 F 1 0.127 60 F 2 0.367 105 F 2 0.663 5.44
GeH
4
26 F 1 0.175 70 F 4 0.415 109 F 3 0.662 6.20
C
2
H
6
28 F 1 0.222 106 F 4 0.472 152 F 4 1.031 4.43
Si
2
H
6
41 F 1 0.228 58 F 5 0.521 179 F 7 0.904 11.1
CF
4
14 F 3 0.109 58 F 1 0.157 94 F 6 0.669 3.84
SiF
4
50 F 1 0.352 58 F 4 0.439 147 F 6 0.919 5.45
SiCl
4
59 F 3 0.309 58 F 5 0.503 172 F8 0.815 13.1
means the formation of SiH
n
+
+e
(n V4). Similar conclusions have also been reached about

He(2
3
S)CH
4
and He(2
3
S)GeH
4
collisions [123,152].
It is seen that the individual de-excitation cross sections for a particular excited atom
are governed by the individual interactions. The de-excitation cross sections of He(2
3
S, 2
1
S,
and 2
1
P) are reasonably interpreted as follows. Two important factors are readily extracted
fromthe semiempirical formula for the Penning ionization cross section, so that the rational
relation of the Penning ionization cross section is obtained:
r
M
/ N
i
IP
1=2
where N
i
is the number of equivalent electrons which can be ionized by the transfer of the
excitation energy of He(2
3
S) and the IP
1/2
involves the electron densities of outer electrons
extending out of the rigid surface of the target molecules, which penetrate into the inner hole
of He(1s
1
). Fig. 16 shows the excellent correlation between the experimental cross sections
and the N
i
IP
1/2
, thus conrming the mechanism of electron exchange interaction [154].
A systematic comparison of the de-excitation cross sections for He(2
1
P) with the
theoretical Penning ionization cross sections using the WK formula shows the importance
of a long-range dipoledipole interaction to determine the transition probabilities and the
strongly attracted trajectories in ionizing collisions, both of which result in large values of
de-excitation cross sections. Photoionization quantum yields of CH
4
and SiH
4
at hv=58.4
nm (21.2 eV) are available for approximate estimation of the products resulting from
He(2
1
P)CH
4
and He(2
1
P)SiH
4
collisions. The quantum yields of more than 95% on a
single photoabsorption suggest that neutral fragmentation of SiH
4
is again much less
important in comparison with Penning ionization in He(2
1
P)CH
4
, He(2
1
P)SiH
4
, and,
presumably, He(2
1
P)GeH
4
collisions. Another feature of the cross sections for He(2
1
P) is
presented in Fig. 17. The ratios of the experimental cross sections to r
WK
values are much
larger than unity for target molecules of smaller photoabsorption cross section, whereas
the ratios approach unity with increasing photoabsorption cross sections. This behavior
reveals the abundance of the dipoledipole interaction relative to the electron exchange
interaction as discussed above [154].
Table 6 De-excitation Cross Sections of He(2
3
S) by CH
4
, SiH
4
, or GeH
4
in Comparison with the Respective Cross Sections for Reaction Products
(in A
2
) (From Refs. 123 and 152.)
He(2
3
S)+CH
4
!
r
M
14
CH
n
+
(n V 4) 12
C*
CH* 0.051
CH
CH
2
, CH
3

He(2
3
S)+SiH
4
!
r
M
18
SiH
n
+
(n V 4)
Si* 0.081
SiH* 0
SiH 0
SiH
2
, SiH
3
0
He(2
3
S)+GeH
4
!
r
M
26
GeH
n
+
(n V 4)
Ge* 0.44
GeH* 0
GeH
GeH
2
, GeH
3

Figure 17 The ratios of the experimental cross sections to the theoretical ones (r
M
/r
WK
) for
He(2
1
P) as a function of photoabsorption cross section (r
abs
) of M at the corresponding energy to
the excitation energy of He(2
1
P). (From Ref. 154.)
Figure 16 Relation of de-excitation cross sections (r
M
) for metastable helium atoms with the
HotopNiehaus formula for (a): He(2
3
S) and (b) He(2
1
S). (From Ref. 154.)
A similar conclusion has been obtained for the de-excitation cross sections of Ne(
3
P
2
,
3
P
1
, and
3
P
0
) by the molecules containing the group IV elements [155]. As shown, the cross
sections are not so strongly dependent on the excited state of neon atoms. Instead, the
dependence of the cross sections on the target molecule is more prominent. A systematic
analysis of the cross sections with respect to the polarizability of target molecules has
provided the physical insight of the mobile state of the r, p, and nonbonding outermost
electrons; the marked dierence in the behavior of the cross section against the target
polarizabilities in Fig. 18 presents the relation of the localized and delocalized electron
characters of the r, p, and nonbonding outermost electrons and the probabilities of
electron exchange.
The cross sections of the de-excitation of Ar
*
(Ar
*
: Ar (
3
P
2
,
3
P
1
,
3
P
0
, and/or
1
P
1
)) by
CH
4
, SiH
4
, and GeH
4
are extremely large [153] (Fig. 19). The dierence in the magnitude
of the cross sections is ascribed to the particular de-excitation mechanisms for the
metastable and resonant excited argon atoms. However, in general, the Penning ionization
is not a major de-excitation process. This is readily seen from the following. The excitation
energy of Ar
*
is smaller than both of the vertical and adiabatic ionization potentials of
CH
4
, so that the Penning ionization of CH
4
is not accessible. In the case of Ar
*
SiH
4
and
Ar
*
GeH
4
collisions, the excitation energy of Ar* is slightly greater than the adiabatic
ionization potential of SiH
4
or GeH
4
, and less than its vertical ionization potential. It is
safely predicted that rendering the Penning ionization requires a strong structural
deformation of a target molecule, which is not accessible with the thermal collisional
energies. As a matter of fact, the ionic products such as CH
n
(0 V n V 4) or H
+
are not
Figure 18 De-excitation cross sections of Ne(
3
P
2
) by M (M=CH
4
, SiH
4
, GeH
4
, CF
4
, and SiF
4
, Ar,
Kr, Xe, H
2
, D
2
, N
2
, O
2
, CO, NO, CO
2
, N
2
O, and SF
6
) as a function of the polarizability of M.
(From Ref. 155.) The target molecules are classied by the type of their outermost molecular
orbitals: r-type (.); p-type (o); and nonbonding ( w ).
observed in mass spectrometric studies for Ar*CH
4
, Ar*SiH
4
, and Ar
*
GeH
4
, as seen in
Table 7. At the same time, the above consideration on the energetics between the excita-
tion energy of Ar
*
and the ionization potential of the target molecule leads to another
insight of the de-excitation mechanism (i.e., the excitation transfer to form the molecular
Rydberg state). The vertical excitation of a molecule with a slightly smaller excitation
energy than the rst ionization potential produces one of the molecular Rydberg states,
which exist with a fairly high density of states in the region slightly below the vertical ion-
ization potential. The density of the molecular Rydberg states increases with the increase in
the excitation energy in the region slightly below the vertical ionization potential of a target
molecule. The probability of de-excitation is enhanced with the increase in the density of
molecular Rydberg states because the number of channels accepting the energy transferred
from Ar
*
is increased.
Thus, it is concluded that the de-excitation of the metastable Ar(
3
P
2
and
3
P
0
) atoms
is ascribed to the nonadiabatic excitation transfer at large intermolecular distance by the
crossing of the intermolecular potential curves between the initial Ar
*
M channel and the
nal ArM* channel, and the de-excitation of the resonant Ar(
3
P
1
and
1
P
1
) to the resonant
excitation transfer by the dipoledipole interaction [153]. This conclusion is compatible
with the result of the above-mentioned conclusions for the de-excitation of He(2
1
P) by Ne
[135].
As a brief conclusion of this section, the cross-section measurements for the de-
excitation of excited rare gas atoms have been best performed using the pulse radiolysis
method. The pulse radiolysis method has provided not only the most reliable cross sections
Figure 19 Comparison of the de-excitation cross sections of excited argon atoms Ar
*
[Ar
*
=
3
P
1
(o) or
1
P
1
(.)] by M (M=CH
4
, SiH
4
, or GeH
4
) with the theoretical cross sections (r
WK
). (From
Ref. 153.)
both for metastable and the resonant atoms, but also several physical aspects of the colli-
sional and molecular insight, so that the research of the collisional de-excitation proceeds
into a new stage of investigation.
ACKNOWLEDGMENTS
The authors thank a number of collaborators for their excellent collaboration, particularly
Dr. N. Kouchi. They also appreciate the early contribution to and the continuous devel-
opment of the pulse radiolysis microwave conductivity/cavity technique by the late Dr. H.
Shimamori.
REFERENCES
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Belgrade, 1989 (Invited Papers); Zigman, V.J., Ed.; University of Belgrade Press: Belgrade,
1989; 242 pp.
2. Hatano, Y. Radiat. Phys. Chem. 1989, 34, 675.
3. Hatano, Y. In Pulse Radiolysis; CRC Press: Boca Raton, Tabata, Y., Ed.; 1991. (Chap. 9).
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M., Ed.; Masson: Paris, 1971; Vol. 15, 7 pp.
6. Hatano, Y. New Exp. Tech. Chem. 1978, 16, 544. in Japanese.
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M.A.J., Eds; . VCH: Berlin, 1987 (Chap. 9).
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Hendry, J.H., Scott, D., Eds.; Taylor and Francis: London, 1987; Vol. 2, 60 pp.
Table 7 De-excitation Cross Sections of Ar(
3
P
2,0
) by CH
4
, SiH
4
, or GeH
4
in Comparison with the Respective Cross Sections for Reaction Products
(in A
2
) (From Refs. 123 and 153.)
Ar(
3
P
2,0
)+CH
4
!
r
M
80
CH
n
+
(n V 4) 0
C*
CH* (A) 0
CH(X) 4.1
CH
2
, CH
3

Ar(
3
P
2,0
)+SiH
4
!
r
M
101
SiH
n
+
(nV4)
Si* 0.27
SiH* (A) 4.0
SiH(X) 4.6
SiH
2
, SiH
3

Ar(
3
P
2,0
)+GeH
4
!
r
M
102
GeH
n
+
(nV4)
Ge* 1.7
GeH* (A) 0.03
GeH(X) 0
GeH
2
, GeH
3

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7
Studies of Solvation Using Electrons and
Anions in Alcohol Solutions
**
Charles D. Jonah
Argonne National Laboratory, Argonne, Illinois, U.S.A.
1. INTRODUCTION
It has long been known that the solvent plays an important part in chemical reactivity. It
can inuence reactivity by altering the energy levels of the reactants and products, by
removing energy from hot modes, by stabilizing intermediates, and by conning reactants.
For these reasons, reactions in solution may be considerably dierent than in the gas phase.
Radiation chemistry highlights the importance of the role of the solvent in chemical
reactions. When one radiolyzes water in the gas phase, the primary products are H atoms
and OH radicals, whereas in solution, the primary species are e
aq
, OH, and H
+
[1]. One
can vary the temperature and pressure of water so that it is possible to go continuously
from the liquid to the gas phase (with supercritical water as a bridge). In such experiments,
it was found that the ratio of the yield of the H atom to the hydrated electron (H/e
aq
)
does indeed go from that in the liquid phase to the gas phase [2]. Similarly, when one
photoionizes water, the threshold energy for the ejection of an electron is much lower in
the liquid phase than it is in the gas phase. One might suspect that a major dierence is
that the electron can be transferred to a trap in the solution so that the full ionization
energy is not required to transfer the electron from the molecule to the solvent.
One can consider two facets of the solvation process, the energetics and the kinetics.
Clearly, the kinetics will not matter if reactions take place on a time scale that is much
faster or much slower than the solvation process. However, if reaction and solvation occur
on the same time scale, the considerable energy changes that the solvation process can
engender will aect the reaction. In fact, exactly what solvent motions take place during
the solvation process may well be important. Thus, it is of interest to understand the ki-
netics of the solvation process.
In a paper, Jortner stated that information about solvation dynamics can be ob-
tained from (1) solvation of the electron, (2) solvation of a dipole, and (3) extracting in-
formation from the rates of electron transfer reaction [3,4]. We have added to these
*
Work performed under the auspices of the Oce of Science, Division of Chemical Science, US-
DOE, under contract number W-31-109-ENG-38.
possibilities the study of the solvation of an anion that is created very quickly, and we
show that some of the characteristics of electron solvation are specic to that species.
Solvation processes are generally studied by observing the shift of an absorption
process or an emission process as a function of time [5,6]. For example, one might excite a
molecule where the excited state is considerably more polar than the ground state. The
solvent would then rearrange the solvent around the excited state to lower the total energy
of the system. One can then observe the shift of the emission spectrum as a function of
time. This is shown pictorially in Fig. 1, with the top showing the system and the bottom
showing the potential curves against the solvent coordinate. This will then lead to a shift
of the emission spectrum towards lower energy. These techniques have been used by many
authors (see, e.g., Refs. [5,6]). The uorescence measurements can make use of the single-
photon-counting technique, and the signal-to-noise and dynamic range of those measure-
ments are much better than for optical absorption measurements. In fact, such experi-
ments are able to separate multiple-exponential processes, something that is not possible
with the absorption measurements.
An alternative technique is to create a ground state species very quickly, by creating
an anion or a cation, or possibly by decomposing a molecule and then observing the
change of its optical spectrum. This technique has the advantage over observing the
relaxation of the excited state in that one is not limited by the uorescence lifetime of
the probe molecule. In the experiments that we will discuss, we will attach an electron to a
benzophenone molecule and then watch the change of the spectrum of the resulting anion.
Fig. 2 shows a cartoon for this process. Note that the absorption will shift towards higher
energies (the blue) for these experiments.
In this paper, we will limit ourselves to the discussion of two types of anions in alcohol
solutions: the benzophenone anion [79] and the solvated electron. One can consider that
these systems are both measurements of the solvation of an anion, if we consider the electron
Figure 1 Cartoon showing solvation and how it will shift the spectrum of a dipolar excited state.
as the simplest anion. We will showthat while there are considerable similarities between the
solvation of the two species, there are also some considerable dierences. We will suggest
that these dierences arise out of the formation mechanism of the electron.
We will not discuss the solvation of the electron in water. While one might expect
that the electron solvation in alcohols should be qualitatively the same as in water, with
only quantitative changes, it turns out that the quantitative changes lead to qualitative
changes in the mechanism. It is usually assumed that the solvated electron is formed in the
excited state, which then relaxes to the ground state, and the solvent reorganizes around
the ground-state electron. This picture seems to hold reasonably well for electrons in
alcohols; however, in water, the solvent relaxation time is suciently fast that the re-
laxation of the excited state of the electron and the reorganization of the solvent occur on
the same time scale, making interpretation dicult.
2. EXPERIMENTAL
The results in this discussion will include those from our laboratory and experiments on
electron solvation from other laboratories. The experiments that were done at Argonne
made use of the stroboscopic pulse radiolysis technique, which will be discussed below.
Experiments from other laboratories have made use of pulse radiolysis and laser photolyis
techniques for the measurement of electron solvation.
Figure 2 Cartoon showing solvation and how it will shift the spectrum of an anion.
The laser photolysis techniques are discussed in detail in the appropriate references.
We will just give a short summary here. The time resolution of the laser photolysis
experiments ranged from 100s of femtoseconds to 2030 ps. An intense light pulse was
used to form the solvated electrons, either by photolyzing the solvent or by photolyzing a
solute in the solvent [1012]. The relaxation of the spectrum was then probed using a
second probe light beam. Walhout and Barbara used an alternative technique [13]. An
ionizing light pulse was used to form the electron. The electron was allowed to relax for
4 ns, and then the solvated electron was optically bleached with a second pulse and the
absorption was probed using a third light pulse.
The experiments that we have carried out make use of the Argonne subnanosecond
pulse radiolysis system, which has been described in detail elsewhere [14]. To summarize, a
30-ps electron pulse is used to create both an electron pump pulse and an optical probe
pulse. To create the probe pulse, a portion of the electron pulse intercepts a cell that is
lled with 1 atm of xenon. This pressure is sucient so that the electrons are traveling
faster than the speed of light in that medium. This generates Cerenkov light, which has the
time prole of the electron pulse and which is a continuum light source where the intensity
increases towards the blue. The portion of the electron beam that is not intercepted by the
gas cell is delayed by a magnet (a 270j magnet or alpha magnet). The Cerenkov light pulse
can be adjusted using an optical delay line so that it can arrive prior to the electron pulse
or up to approximately 3 ns after the pulse (maximum time range of approximately 3.9 ns).
For the experiments that measure the solvation of the electron in an alcohol,
dierent neat alcohols were placed in a ow cell and the kinetics at dierent wavelengths
and the evolution of the spectra were observed [1517]. Kinetics were determined to the
blue side of the solvated electron spectrum. The temperature could be lowered to provide
data over a range of temperatures. The lower-temperature experiments all utilized n-
propanol or 2-propanol because they have a long liquid range [18].
Additional experiments were done in mixtures of alcoholalkane [16,17]. The spectra
and kinetics were measured in mixtures of 1-propanoln-hexane. Some experiments were
done in cyclohexane, where the behavior was qualitatively similar; however, the exact con-
centration where spectra and kinetics changed depended on the alkane [16]. Additional
experiments observed the shift of the nal spectrum of the solvated electron in supercritical
ethanemethanol mixtures. These experiments were done using standard pulse radiolysis
techniques and thus we were unable to observe the kinetics [19].
Anion-solvation experiments were done using benzophenone as a probe molecule.
These experiments were suggested by Bernard Hickel and were based on work of Marig-
nier and Hickel and Ichikawa et al. in low-temperature alcohols [79]. The concentration
of benzophenone was in the range of 0.25 M. This concentration was shown to be suf-
cient so that it would react with all of the solvated-electron precursors; thus, virtually no
solvated electrons would be formed under these conditions [20]. The data were analyzed by
considering the time dependence of the spectra and the kinetics and evaluating a global t
for these data [20,21]. These experiments were done in a series of alcohols, as a function of
temperature, and in alcoholalkane mixtures.
The solvation processes for the anion systems were simulated using both simple ball
models and more representational models of the solvent and solute [14,22].
3. RESULTS AND DISCUSSION
The measurement of the solvation of an aromatic anion and the measurement of the
solvation of an electron in alcohols have quite a bit in common. They both observe the
response of the solvent to the sudden creation of an anion in the bulk of the solution.
Thus, one might expect that the nal states would be similar. However, there may well be
considerable dierences in the initial states, which then may well lead to changes in the
solvation process.
The electron will be solvated in a region where the solvent molecules are appropri-
ately arranged. There must be a cluster of electrons of a size of 45 to support the for-
mation of the solvated electron from the results of Gangwer et al., [23], Baxendale [24,25],
and Kenney-Wallace and Jonah [16]. This behavior does not depend on the specic
alcohol or alkane and even occurs in supercritical solutions, as has been shown in ex-
periments done using mixtures of supercritical ethanemethanol mixtures [19]. Experi-
ments have also shown that the thermodynamically lowest state might not be reached. For
example, the experiments of Baxendale that measured the conductivity of the solvated
electron in alcoholalkane mixtures showed that when there was a sucient concentration
of alcohols to form dimers, there was a sharp decrease in the mobility of the electron
[24,25]. This result showed that the electron was at least partially solvated. However, the
conductivity was not as low as one would expect for the fully solvated electron, and the
fully solvated electron was never formed on their time scale (many microseconds), a time
scale that was suciently long for the electronalcohol entity to encounter sucient
alcohols to fully solvate the electron. Similarly, the experiments of Weinstein and Fire-
stone, in mixed polar solvents, showed that the electron that was observed depended on
the initial mixture and would not relax to form the most fully solvated electron [26].
The situation for the benzophenone molecule would be expected to be considerably
dierent. The major driving force for the attachment of the electron is the electron anity
of the benzophenone molecule. The arrangement of the solvent around that molecule will
provide only a perturbation to that energy. Thus, one will observe an average of the
solvent structures around the benzophenone and not just solvent arrangements that are
optimal to trap the electron. Similarly, because the charge is more delocalized on the
benzophenone molecule, the alcohol molecules might not be so strongly aligned, so that
the alcohol molecules will be able to rearrange and reach the lowest energy conguration.
We shall discuss separately the results for electron solvation and anion solvation at
room temperature in dierent alcohols to provide a basis for the discussion of solvation
mechanisms. This will be followed by a discussion of solvation at lower temperatures and
in alcoholalkane mixtures to further highlight the similarities and dierences between
anion and electron solvation.
3.1. Electron Solvation at Room Temperature
There have been many experiments on electron solvation at very low temperatures, and
the results depend on the temperature range and alcohol. For n-propanol, which has a
very long liquid range, Baxendale and Wardman showed that the solvation behavior
changes markedly from 110 to 120 K [27]. At the higher temperatures, kinetics and spec-
tral changes are similar to what are seen at room temperature, while at lower temper-
atures, the results are similar to what are observed in glasses. The original experiments on
electron solvation in alcohols near room temperature were carried out by Chase and Hunt
[28]. In their experiments, they used their stroboscopic pulse radiolysis system to determine
the kinetics of the electron solvation. Those experiments were followed by further pulse
radiolysis experiments that obtained similar results [15,17]. With the advent of short-
pulsed lasers, several groups explored the solvation of the electron in alcohols. A summary
of the pulse radiolysis data was given by Kenney-Wallace and Jonah [16], and a summary
of the laser data has been given by Walhout and Barbara [13].
If one observes the blue of the absorption maximum, the signal appears to consist of
a fast rise followed by a slower growth. We are concerned here with the slower growth,
because it arises from the relaxation of the solvent around the electron. This behavior was
seen in both the photolytic and radiolytic formation of the electron. The data of Walhout
and Barbara are a bit more complex in this time period, because one has a bleach followed
by a recovery of the absorption of the electron (however, not all the absorption is recov-
ered, suggesting that the electron reacts with the solvent after the photoexcitation) [13]. A
summary of the measured kinetics from both laser and pulse radiolytic experiments are
given in Fig. 3. As we can see from this gure, the rate of the slow growth does not appear
to depend on the mode of formation. Early results suggested that there were dierences
between the rate of electron solvation for the dierent methods of electron formation, but
it has been suggested by Sander et al. that the dierences arose from the data analyses of
some of the early laser data [11], because the earlier analyses of the laser-ash-photolysis
data did not separate the slow growth process from the fast component, which would have
been instantaneous on their time scale.
Fig. 3 displays the solvation time of the electron (using open symbols) plotted
against the longitudinal relaxation time. The results were plotted against the longitudinal
relaxation time because that is the time scale that some continuum models would have
suggested. Note that the rates are comparable to those seen for the solvation of an anion,
and considerably faster than those measured for dipole solvation. The anion data will be
discussed below.
The shift of the spectrum has been well discussed previously. The early pulse
radiolysis data suggested that the kinetics at 1300 nm [28] matched the kinetics in the
blue [16], which led to the description of the kinetics as a two-state problem. However, the
results measured by Chase and Hunt, where the kinetics at 1050 nm were considerably
slower than the kinetics at 500 and 1300 nm, suggested that the kinetics were more
Figure 3 Solvation time in alcohols of the electron and the benzophenone anion, plotted versus the
longitudinal relaxation time s
1
. (The dipole data are from Refs. [5,6].)
complicated than a two-state model would predict [28]. Some authors have suggested the
existence of an approximate isosbestic point [12]. It seems to be clear that the response
observed well to the blue of the peak does not depend on wavelength [16].
3.2. Anion Solvation
Anion solvation has been studied by observing the shift in the absorption spectrum of the
benzophenone anion in various solvents and as a function of temperature. The benzo-
phenone anion was formed from the reaction of the benzophenone molecule and a
precursor to the solvated electron. Approximately 0.25 M benzophenone is put into the
solution so that all the presolvated electrons will react with the benzophenone and
virtually none will form the solvated electron. This process occurs much more quickly
than the solvation processes that are observed [14,20].
The rst experiments were done in a series of primary alcohols at room temperature.
In Fig. 4, we show the spectra as a function of time at room temperature at dierent times
in n-octanol. Similar data are seen in all the primary alcohols, and the nal solvated
spectrum is similar for all of the alcohols, suggesting that nal solvated anion state is
similar in all primary alcohols.
One of the models that has had considerable success for predicting solvation
processes of dipoles in non-hydrogen-bonded solvents is the dielectric continuum model
[5,14]. In this model, the amount of solvation will depend on the dipole densitythat is,
the molar concentration and strength of dipoles. While the position of the absorption
maximum is not directly related to the energy of solvation that a molecule experiences, one
would expect the two to be very strongly correlated. However, for the three dierent
Figure 4 Spectra of the benzophenone anion in n-octanol as a function of time after the generation
of the anion.
primary alcohols considered here, the dipole density changes by more than a factor of 2,
with the highest density for the butanol alcohol and the lowest density for the decanol
solvent, and the maxima of the spectra of the solvated anion do not change. We interpret
these results to mean that it is the local concentration of dipoles around an anion that
dominates the solvation and not the concentration of the dipoles in the bulk of the
solution.
We have also carried out experiments in secondary alcohols. For example, Fig. 5
shows the spectra in primary and secondary octanol (1-octanol vs. 2-octanol). These data
show that while the initial spectra are approximately the same in the two alcohols, the nal
spectra are considerably dierent. There is much less shift in the absorption spectrum in
the 2-octanol, suggesting that 2-octanol is less eective at solvating the benzophenone
molecule.
We suggest that in a secondary alcohol, there will be steric hindrance, which will
limit the number of molecules that can get near the ion. This is shown, cartoon fashion, in
Fig. 6. As one can see, the steric factors might well limit the ability of the alcohols to pack
around an anion.
To test these suggestions, simple Monte Carlo and molecular dynamics simulations
were carried out [22]. These explored the potential energy of a charge in the presence of
solvent molecules of dierent forms. The form of these approximations is shown in the
reference. These simple systems embody the primary characteristics of the present system.
The results showed that the solvation energy (the eld at the charge) does not depend on
the length of the solvent molecule but on the orientation of the dipole. If the positive end
of the dipole is at the end of the molecule, solvation will be strong. This agrees with the
experimental results that show that the nal spectra are very much the same in all primary
alcohols.
Figure 5 Spectra of the benzophenone anion in primary and secondary n-octanol.
Simulations were done where the dipole is reversed in the solvent molecule. This is
equivalent to making measurements in acetonitrile. The calculations suggested that there
would only be weak solvation in acetonitrile, despite the fact that acetonitrile is far more
polar than any of the alcohols that we have measured. This fact is indeed borne out
experimentally. The spectrum of the benzophenone anion is considerably to the red of the
spectrum of the benzophenone anion in any of the alcohols that we have measured. In
addition, there is no evidence for any shift of the spectrum in the time scale that we
observe. This lack of shift may not be surprising, because experiments in acetonitrile
suggest that the solvation time is very fast. Thus, any relaxation that is going to take place
will have occurred on the time scale of the present experiments.
Typical kinetics for the solvation of an anion in 1-octanol are seen in Fig. 7. While an
approximate isosbestic point has been seen for the solvation of the electron in an alcohol,
this gure shows there is nothing approaching an isosbestic point for this process. The
kinetics are dierent at dierent wavelengths, and even include both a growth and decay.
The kinetics were determined by tting the time proles and spectra at dierent times.
The results of these analyses are seen in Fig. 3, along with the data for the solvation of the
electron in the same solvents, as discussed above. We see that the solvation time for the
anion is longer but of the same order of magnitude as the solvation time for the electron,
and it is much shorter than would be predicted for dielectric relaxation.
3.3. Temperature Dependence
Solvation takes place through multiple processes, each with dierent energy requirements.
By making measurements at dierent temperatures, one can begin to separate the multiple
processes and possibly shift which processes are dominant. For these reasons, temper-
Figure 6 Cartoon of the eect of structure on benzophenone anion solvation.
ature-dependent measurements have always been an important technique for under-
standing fundamental reaction pathways. As has been mentioned previously, the spectral
and kinetic behavior of the solvation process alters drastically in n-propanol between 110
and 120 K [27]. There have also been studies of the activation energy of solvation for
dipolar systems, which we will compare to the present data. We will rst discuss the anion-
solvation measurements, then the electron solvation measurements, and then compare the
two dierent chemical systems.
Anion Solvation as a Function of Temperature
In Fig. 8 (top), we see the temperature dependence of the rate of solvation of the ben-
zophenone anion in primary and secondary propanol and n-butanol as a function of
temperature [21,29]. As one would expect, the solvation rate is slower in n-butanol than it
is in n-propanol; however, as we can see from the slope of the Arrhenius plot, the acti-
vation energies are about the same, both having an activation energy of approximately 22
kJ/mol. The activation energy for solvation of the anion in 2-propanol is considerably
lower, 16 kJ/mol. These values are similar to the energy required to break a hydrogen
bond in these systems, of 25F3 kJ/mol for the primary alcohols and 17F3 kJ/mol for 2-
propanol [30]. The ordering of the activation energies is reasonable in that steric hindrance
will decrease the hydrogen bonding in the secondary alcohol in comparison to the primary
alcohol. The similarity of the solvation energy to the activation energy for hydrogen-bond
breakage would suggest that hydrogen-bond breakage is important in the solvation
process; however the correlation with s
2
, the second dielectric relaxation time, which is
often attributed to the rate of rotation without breaking hydrogen bonds, is not consistent
with that picture [31].
Figure 7 Time proles of the absorption of the benzophenone anion as a function of wavelength.
Figure 8 (a) Temperature dependence of the solvation of the benzophenone anion in primary and
secondary propanol and n-butanol. (b) Temperature dependence of the solvation of the electron in
n-propanol and 2-propanol.
If one compares the log of the solvation time to the log of viscosity, the two primary
alcohols fall on the same straight line and this line has a slope of 1. The 2-propanol, while
correlated with viscosity, does not show a linear dependence [21].
Temperature Dependence of Electron Solvation
These results can be compared to the temperature dependence that has been seen in
electron solvation (see Fig. 8, bottom) [18,28]. We rst note that the dependence of the
solvation time on temperature is quite dierent for 1-propanol and 2-propanol. It appears
as if the activation energy for 2-propanol is considerably higher than 1-propanol, which is
the reverse of what was observed for the solvation of an anion or for the hydrogen-bond
energetics. The activation energy for solvation in 1-propanol is 14.4 kJ/mol, which is less
than the energy for hydrogen-bond breakage, while the activation energy for 2-propanol is
21 kJ/mol, which is considerably higher than the activation energy for anion solvation and
considerably higher than the energy of a hydrogen bond.
It has been suggested that the electron will solvate in a preexisting structure in the
liquid such as a cyclic tetramer or pentamer [16,23]. It is known that these types of
structures are quite common in alcoholalkane mixtures. Because the electron is dissolved
in the preexisting structure that has an appropriate structural arrangement, it might not be
necessary to break the hydrogen bonds to solvate the electron. In 2-propanol, exper-
imental data suggest that in dilute alcohol solutions, the alcohol tends to form polymer
chains rather than cyclic structures. This means that to create the nal electron structure,
one will need to break polymeric hydrogen bonds and allow the alcohols to rearrange to
create a structure around the electron. This then requires the breaking of hydrogen bonds
and the higher activation energy results from that fact.
3.4. Concentration Dependence of Solvation
Concentration Dependence of Anion Solvation
Figs. 9 and 10 show the shift of the spectra and the dierent kinetics that occur as a
function of alcohol concentration in the benzophenone system in propanolhexane
mixtures. These results show that there is a fast absorption, which is due to the formation
of the benzophenone anion. This absorption is then followed by a slow growth. This
growth is much slower than what is seen in the neat alcohol, and the rate of the growth
depends on the concentration of the alcohol in the propanolhexane mixture. Fig. 11
displays the rate of growth as a function of concentration at two dierent wavelengths, 750
and 800 nm. The rate at 800 nm is approximately twice as fast as the rate at 750 nm. If the
benzophenone anion is more solvated, the spectrum will be more blue-shifted. Presumably,
the more deeply solvated anions will have more alcohols near them, and it should take
longer to solvate. However, one does not expect this to be a simple function, because the
spectra will be both homogeneously and heterogeneously broadened. The dierent rates of
solvation as a function of wavelength are consistent with this result. The measured rate
constants are consistent with what one would expect for the rate of an alcohol molecule
diusing to the anion and aligning itself (reacting).
Concentration Dependence of Electron Solvation
The results for the solvation of the electron in mixed systems are greatly dierent from the
results for the anion solvation. All evidence, which we summarize below, is consistent with
Figure 9 Spectral dependence of the benzophenone anion as a function of time at 0.15 M propanol
in n-hexane.
Figure 10 Solvation kinetics of the benzophenone anion in propanolhexane mixtures measured at
800 nm.
the picture of an electron nding an appropriate location and then rearranging the solvent
in the vicinity of it and not solvating further by bringing alcohol (or other solvent) mo-
lecules into the inner shell around the electron.
In the experiments of Weinstein and Firestone [26], it was shown that the spectrum
of the electron in mixed solvents depends on the mixture of the two components, for
example, an alcohol and an ether. If complete relaxation were possible, one would expect
that the solvent molecules would interchange and the result would be the lowest energy
conguration. This does not appear to occur.
In experiments done by Baxendale [24] and Baxendale and Sharpe [25] in mixed n-
propanolhexane systems, it was found that at low concentrations of alcohol, a solvated
species was formed; however, it was not the solvated electron. The existence of the
solvated species was determined by the decrease in mobility of the electron in the solvent.
The mobility never decreased to the level that would be expected for the solvated electron
and no evidence of the solvated electron spectrum was detected.
Experiments done by Kenney-Wallace and Jonah showed a fast initial solvation of
the electron followed by a shift/increase of the spectrum towards the blue on a time scale
that is similar to (but somewhat slower than) the rate of the solvation of the electron in the
neat alcohol [16,17]. There was no long-term alteration of the spectrum on the time scale
that would be needed to allow an alcohol molecule to diuse to the solvated electron (a
nanosecond or two, as seen in the kinetics for the benzophenone anion solvation).
The results of Baxendale and Wardman, Kenney-Wallace and Jonah, and Gangwer
et al. are all consistent with the idea that there must be preformed traps in the solution
[16,2426]. Further evidence consistent with this view arises from experiments of Dimi-
trijevic et al., who measured the yield and the spectrum of the solvated electron as a
Figure 11 Rate of the solvation of the benzophenone. First-order rate constant at 800 nm is
1.1510
10
(Msec)
1
and at 750 nm the rate is 6.810
9
(Msec)
1
.
function of temperature in mixtures of supercritical ethanemethanol [19]. As one raised
the temperature, the maximum of the absorption spectrum of the solvated electron in the
mixture shifted to the red the same amount as did the spectrum of the electron in neat
alcohol. The amount of absorption decreased at higher temperatures. Above 110jC, the
absorption spectrum disappeared in the alcoholalkane mixture. In a solution, an electron
will solvate where there exist suciently large clusters of alcohols to solvate the electron or
it will react with the cations in the solution. The decrease in absorption as a function of
temperature was interpreted to mean that the concentration of alcohol-molecule clusters
capable of solvating the electron decreased at higher temperatures. At higher temper-
atures, the number of clusters that are suciently large to support the solvated electron
decreased, and at 110jC, the probability of the electron nding such a cluster decreased to
such a level that no solvated electrons were formed.
4. SUMMARY
While the solvated electron may be considered the smallest and simplest anion, its
solvation behavior in alcohols is not the same as an anion. An anion can solvate by
attaching solvent molecules from the bulk of the solution, the solvated electron does not
do this. A solvated electron is formed making use of particular structures in the solvent so
the arrangement of solvent molecules is not random. This means that we are observing a
small subclass of the solvent structure when we observe electron solvation. Electron
solvation can be an excellent probe for structure of the liquid because of this characteristic.
This fact was utilized in estimating the size and structures of alcohol molecules in
supercritical ethanemethanol mixtures [19]. However, the solvation behavior is not
necessarily characteristic of the behavior that one would expect for an anion in the
solvent. The driving force for the attachment of the electron to a large aromatic molecule
will be the electron anity of the solute molecule and not the solvent structure. This means
that the anion that is quickly produced will be initially probing the average.
While noting the dierences in behavior between electron solvation and anion
solvation, we cannot forget the similarities. The activation energies for solvation seem to
be related to the strength of the hydrogen bond in the solvent, when a solvent rearrange-
ment will take place. In addition, the solvation times are closely related to the dielectric
relaxation time s
2
, the time assigned to molecular rotation without breaking hydrogen
bonds, rather than s
1
, the time for the rotation requiring hydrogen-bond breakage. The
latter is the time that correlates with the rate of dipole solvation [5]. Whether this is a char-
acteristic of the solvent or the long-range forces that occur with anion solvation is not clear
at the present.
In this discussion, I have intentionally not discussed the solvation of the electron in
water. These results are quite confusing because of the overlap of the electronic relaxation
of the excited solvated electron and the rearrangement of the solvent. In an alcohol, these
terms are well separated and so discussion is simplied. In addition, we are not aware of
any study on the solvation of an anion in water.
There are many future roads for research that can greatly illuminate the physical
processes. It would be interesting to observe the solvation of a neutral species that is
formed from a negative species by photoionization. One might well expect solvation to be
faster for this system because the solvent molecules near the anion/neutral could rearrange
without breaking hydrogen bonds. The solvation of an anion primarily rearranges
molecules that are hydrogen bonded to other solvent molecules.
Supercritical solutions also provide a large and interesting collection of phenomena
that can be probed using these techniques. The greater uctuations in these solvents may
increase the rate of solvation because of the larger number of possible states that can exist.
Solvation is an important component of all reactivity and now it is possible to gain a
clearer insight into these processes. Hopefully, this will continue in the years ahead.
REFERENCES
1. Spinks, J.W.T.; Woods, R.J. An Introduction to Radiation Chemistry; 3rd Ed; 1990.
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12260.
3. Rips, I.; Klafter, J.; Jortner, J. J. Chem. Phys. 1988, 89, 4288.
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5. Maroncelli, M. J. Mol. Liq. 1993, 57, 1.
6. Simon, J.D. Acc. Chem. Res. 1988, 21, 128.
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8. Marignier, J.L.; Hickel, B. J. Phys. Chem. 1984, 88, 5375.
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10. Hirata, Y.; Murata, N.; Tanioka, Y.; Mataga, N. J. Phys. Chem. 1989, 93, 4527.
11. Sander, M.; Brummund, U.; Luther, K.; Troe, J. Ber. Bunsen-Ges. 1992, 96, 1486.
12. Shi, X.; Long, F.H.; Lu, H.; Eisenthal, K.B. J. Phys. Chem. 1995, 99, 6917.
13. Walhout, P.K.; Barbara, P.F. Ultrafast Processes in Chemistry and Photobiology, 1995; 83 pp.
14. Lin, Y.; Jonah, C.D. Understanding chemical reactivity. 1994, 7, 137.
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18. Zhang, X.; Jonah, C.D. Chem. Phys. Lett. 1996, 262, 649.
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22. Lin, Y.; Jonah, C.D. Chem. Phys. Lett. 1995, 233, 138.
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8
Electrons in Nonpolar Liquids
Richard A. Holroyd
Brookhaven National Laboratory, Upton, New York, U.S.A.
1. INTRODUCTION
Excess electrons can be introduced into liquids by absorption of high-energy radiation, by
photoionization, or by photoinjection from metal surfaces. The electrons chemical and
physical properties can then be measured, but this requires that the electrons remain free.
That is, the liquid must be suciently free of electron attaching impurities for these
studies. The drift mobility as well as other transport properties of the electron are
discussed here as well as electron reactions, free-ion yields, and energy levels.
Ionization processes typically produce electrons with excess kinetic energy. In liquids
during thermalization, where this excess energy is lost to bath molecules, the electrons
travel some distance from their geminate positive ions. In general, the electrons at this
point are still within the Coulombic eld of their geminate ions and a large fraction of the
electrons recombine. However, some electrons escape recombination and the yield that
escapes to become free electrons and ions is termed G
. Reported values of G
for molec-
ular liquids range from 0.05 to 1.1 per 100 eV of energy absorbed [1,2]. The reasons for this
20-fold range of yields are discussed here.
Electrons in nonpolar liquids are either in the conduction band, trapped in a cavity
in the liquid, or in special cases form solvent anions. The energy of the bottom of the
conduction band is termed V
0
. V
0
has been measured for many liquids and its dependence
on temperature and pressure has also been measured. New techniques have provided quite
accurate values of V
0
for the liquid rare gases. The energies of the trapped state have also
been derived for several liquids from studies of equilibrium electron reactions. A
characteristic of the trapped electron is its broad absorption spectrum in the infrared.
Electron attachment rates have been measured for numerous solutes. Many of these
studies were limited to three solvents: cyclohexane, 2,2,4-trimethylpentane, and tetrame-
thylsilane (TMS), and those rates are discussed here. What to expect in other liquids can
be inferred from these results. Considerable insight has been gained into certain reactions.
Equilibrium reactions of electrons are particularly interesting since they provide informa-
tion not only on energy levels, as mentioned above, but also on the partial molar volume
of trapped electrons. This has led to a better understanding of the mechanism of electron
transport.
This chapter presents the current understanding of electrons in nonpolar liquids.
Experimental as well as theoretical studies are discussed. For further detail than is pro-
vided here, the reader is referred to recent books on the subject [3,4] as well as references
cited herein. Some questions still remain due largely to the theoretical diculties of de-
scribing a quantum particle in a disordered environment. The future will hopefully bring
new discoveries and revelations that will answer these questions. Finally, we discuss current
applications of nonpolar liquids to indicate where future uses may develop.
2. ELECTRON ESCAPE AND RECOMBINATION
An important consideration in understanding a radiation chemical mechanism or predict-
ing the outcome of a radiation experiment is knowing the yield of free electrons or G
, the
number of ion pairs produced per 100 eV absorbed. The free ion yield is aected by the
density of ionization along the track of the ionizing particle. The highest yield is observed
for high-energy electrons, typically 12 MeV, which result in well-separated clusters of a
few ionizations each. An alpha particle creates a dense column of ionization and ion yields
are very low. X-rays show intermediate behavior. Other factors like molecular structure,
temperature, applied eld, pressure, and density also aect G
.
Making sense of free ion yield data requires rst knowing what is meant by the free
ion yield. Free electrons are those that escape initial spur or track recombination and are
therefore diusing in the bulk and can react with other species in a homogeneous fashion.
The escape process can be considered to have two steps. First, the electrons released by
ionizing the solvent molecules lose energy in scattering events and, in the process, travel
some distance, r, from their positive ions. The electrons may lose energy to vibrational
modes, but a signicant fraction of the range occurs while the electron has lower, near
thermal, energy. In general, there will be a distribution of ranges D(r) and the mean
thermalization range is designated by b. For most nonpolar liquids, the electrons after
thermalization will still be within the Coulombic eld of the positive ions, equal to e
2
/er,
where e is the dielectric constant. Consequently, the fraction escaping is low.
In the second step, the thermalized electrons will either recombine with the ions in the
track or spur or escape. The yield of free electrons is the integral of the product D(r) P(r)
times the number of electronion pairs formed initially in the spur or track, G
tot
, where
P(r) is the probability of escape. For a single ion pair, P(r) is given by [5]:
Pr exp e
2
=ek
B
T

1
The initial yield, G
tot
, is not known exactly for molecular liquids. However, the
fraction of electrons that escape geminate recombination increases with the applied electric
eld and extrapolating such results to high eld gives G
tot
=4.0 for neopentane [6], 3.1F0.3
for TMS [7], and 4.5 for Ar [8]. A value for G
tot
of 4.0 was obtained for cyclohexane by
measuring the yields of methyl radicals formed in the reaction of electrons with methyl
chloride and methyl bromide [9]. High concentrations of these solutes were used (up to 0.5
M) in order to compete with geminate recombination. An analysis by Jay-Gerin [10] of
free ion yield data led to an average G
tot
value of 3.7F0.5 for typical hydrocarbons. Others
have suggested that G
tot
may vary considerably from liquid to liquid [11].
Fast pulse radiolysis studies have shown that geminate recombination occurs on the
picosecond time scale [12,13]. Bartczak and Hummel [14] predicted that for n-dodecane,
82% of the geminate ions still remain at 5 psec for 1 MeV irradiation. Future accelerators,
with pulses of a few picoseconds length, may soon provide experimental measurements of
G
tot
directly.
2.1. G
fi
for Minimum Ionizing Radiation
For minimum ionizing radiation, where the ionization events are widely separated, the
value of G
at room temperature correlates with the electron mobility, l

D
[1,10].
Fig. 1 illustrates this dependence for representative liquids. Typically, G
and l
D
are
low for n-alkanes, n-alkenes, and aromatics and high for branched compounds with many
methyl groups like neopentane. For l
D
>0.1 cm
2
/Vs, the yields for alkanes follow
reasonably well a relationship suggested by Jay-Gerin [10]:
G
a l
D

x
2
Implicit in such a dependence is the recognition that scattering lengths of thermal and
epithermal electrons are similar. A least-squares t of the data for compounds containing
only hydrogen and carbon leads to the solid line shown in Fig. 1 for which a = 0.25 and
x = 0.33, for l
D
in cm
2
/Vs.
Fig. 1 includes points for ethane and propane at 298 K for which G
= 0.94 and 0.43

ions/100 eV, respectively [16]. The electron mobilities for these liquids at this temperature
are quite high. At even higher temperatures, in the supercritical uid, G
and l
D
for ethane
and propane are still higher [20,21]. On the other hand, at low temperatures near the
boiling points, the yields of free ions as well as the mobilities in these liquids are quite low
( G
= 0.16 for ethane for example), and points for these liquids then would be on the left
side of the gure.
The data for compounds containing a silicon or germanium atom fall on a lower line
(dashed) in Fig. 1 for which a = 0.12 and x = 0.34 in Eq. (2). That is, for any given
mobility value, compounds containing a heavier atom have a lower free ion yield than that
given by the line for alkanes [15]. A lower G
means a shorter mean thermalization range,

suggesting that scattering of epithermal electrons is stronger when silicon or germanium
Figure 1 Loglog plot of free ion yield vs. electron mobility in nonpolar liquids. (From Refs. 2 and
1519.) Numbers refer to liquids listed in Table 2.
atoms are present. The points for benzene and toluene are also below the line for alkanes.
While Eq. (2) is a rough prediction of how G
changes with mobility, it fails in some cases.

For example, when pressure is applied to 2,2-dimethylbutane and 2,2,4-trimethylpentane,
l
D
increases yet G
decreases [22]. However, for n-pentane and TMS, Eq. (2) predicts the
changes in G
with pressure quite well.

Free ion yields generally increase with increasing temperature, indicating that the
mean thermalization distance, b, increases. Since the density, d, decreases with increasing
temperature, several authors have examined how the product, bd, changes. In the case of
n-alkanes and benzene, this product is fairly constant over a large temperature range [17].
This same study also found that at 296 K, bd is almost the same for the alkanes from C
4
to
C
14
. For the pressure study mentioned above, free ion yields were found to decrease with
increasing pressure, yet the product, bd, remained quite constant for all six liquids studied
[22].
2.2. G
fi
for X-rays
Yields of free ions for exposure to x-rays are less than for high-energy electrons.
Interaction of x-rays with nonpolar liquids occurs largely by the photoelectric eect, with
Compton scattering becoming important as the photon energy increases. Both events
release electrons. The photoelectron energy is given by the x-ray energy less the binding
energy, which for carbon is 284 eV. For hydrocarbons, photoelectrons from the k-shell of
carbon will dominate.
Results for x-rays are shown in Fig. 2. G
has been measured for three liquids for x-

rays of 1.6- to 30-keV energy [2325]. The gure also includes points for minimum ionizing
Figure 2 Free ion yields for n-hexane, 2,2,4-trimethylpentane, and 2,2,4,4-tetramethypentane as a
function of x-ray energy. Points are experimental [2325]. Dashed lines are theoretical [26]; dotted
line is theory [27]. Reproduced by permission [28].
radiation at 2 MeV. There are very large changes in yield with energy. For 2,2,4,4-
tetramethypentane, G
changes from 0.83 to 0.12 ions/100 eV. The probability of escape is

only 3% in the 25 keV range.
The lower yields for x-rays come about as a result of the high rate of energy loss of
the photoelectrons resulting in a high density of ionizations along the track of the electron.
This rate of energy loss depends on the energy of the photoelectrons. For a 30-keV
electron, ionizations occur on average 24 nm apart, while for a 2-keV electron, ionizations
occur 2.9 nm apart. Thus there is overlap of ionizations because the thermalization ranges
of the secondary electrons are comparable to the distance between ionizations. A
secondary electron will sense several positive ions along the track, thus increasing the
probability of recombination in the track.
Theoretical calculations of the free ion yields have been made as a function of the
electron energy. These calculations start with a given track structure for the position of the
positive ions and a distribution of distances for the secondary electrons. The charges are
then allowed to diuse in the electric eld due to all the other charges. Electrons either
recombine with positive ions or escape. The lines in Fig. 2 were calculated in this way. The
dashed lines are for n-hexane and 2,2,4-trimethylpentane. In this case, a Gaussian
distribution of electron separation distances was assumed, with the mean thermalization
ranges, b, shown on the gure [26,29]. For the dotted line, an exponential distribution with
an average thermalization range of 26.5 nm was assumed [27]. The computer simulations
agree quite well with the experimental measurements.
2.3. G
fi
for Alpha Particles
The few studies that have been made indicate that the free ion yield for exposure of liquids
to alpha particles is quite small. For hydrocarbons, G
is very small, 0.005 per 100 eV

[30,31]. Theoretically, a zero yield is expected for cylindrical geometry and alpha particles
create such a track. The low yields in hydrocarbons can be attributed to those electrons on
the tail of the distribution that thermalize some distance from the track; these are often
called delta rays. For liquid rare gases, the yields are higher; for example, the zero eld
yield is 0.16 per 100 eV for Xe [32] because the thermalization ranges are much longer.
3. ENERGY OF THE QUASI-FREE ELECTRON
The existence of a band of states in which the electron is quite mobile and its wave
function is extended is common to all nonpolar liquids. The energy of the lowest state in
this band relative to vacuum is designated V
0
. Values of V
0
for nonpolar molecular liquids
range from +0.2 to 0.75 eV at room temperature [2]. Some representative values are
given in Table 1. When V
0
is low in energy, there is usually little trapping and the electron
mobility is high. Conversely, when V
0
is high, the trap state is likely to be favored and the
mobility is low. When V
0
is positive, the electron favors the vacuum over the liquid
energetically. Emission of electrons into the vacuum occurs readily for liquids for which V
0
is positive like n-hexane (V
0
= 0.1 eV) [35,36]. For liquid helium, V
0
is +1.3 eV and the
electron resides in a bubble of radius 1.4 nm [37].
The energy of the V
0
state is usually considered to be the dierence between two
terms: an attractive polarization energy, U
P
, and a kinetic energy term, T
0
. Conceptually,
this energy is like the energy of the ground state of an electron in a potential well, where
the walls of the well are the impenetrable hard sphere surfaces of the molecules of the uid.
When these walls come closer, the energy T
0
will increase, which explains why V
0
increases
with density for liquids. For example, V
0
increases with decreasing temperature for various
hydrocarbons [38]. When pressures of 2.5 kbar are applied to hydrocarbons, increases in
V
0
of a few tenths of an electron volt are observed [39]. Various theories have been used to
calculate V
0
(see below).
Several methods have been employed to measure the energy of this state in nonpolar
liquids. The methods fall into three categories: the change in work function of a metal
when immersed in the liquid, photoionization, and eld ionization. Of these, the latter, in
which eld ionization of high-lying Rydberg states is utilized to locate V
0
, has in recent
years provided what are considered to be the most accurate values of V
0
in uid Ar, Kr,
and Xe.
In the photoelectric method, V
0
is obtained as the change in work function, /, of a
metal when immersed in the liquid. Thus V
0
is given by the dierence in work functions:
V
0
/
liq
/
vac
3
This method was rst used to determine V
0
in liquid Ar [40] and was later applied to liquid
hydrocarbons [38,4143] as well as to supercritical hydrocarbons like ethane [4446]. Most
of the data available on V
0
for nonpolar liquids were obtained by this method.
In a variation of the photoelectric method, V
0
can be determined by measuring the
emission of electrons from the liquid into the vacuum. Even when V
0
is negative, electrons
can penetrate this barrier and be collected in the gas phase [35,36,47]. Borghesani et al. [48]
used this technique and from the time evolution of the current reaching the anode for a
sample of liquid Ar at 87 K found V
0
to be 0.126 eV. This is in excellent agreement with
the value of 0.125 eV given by Eq. (6) (see below) for this density (2.09 10
22
cm
3
)
using the eld ionization technique.
When molecules are photoionized in a liquid, there is a lowering of the ionization
threshold, E
th
, due to both the sudden polarization of the liquid by the ion E
pol
and V
0
.
Thus:
E
th
IP E
pol
V
0
4
Astudy of the photoionization of tetramethyl-p-phenylenediamine (TMPD) in solution [49]
showed the dependence of the wavelength of ionization onset on the energy V
0
of the sol-
Table 1 Energy Levels of Electrons at 298 K
Solvent V
0
(eV) DG
soln
(e)
n-Hexane 0.10 0.33
Cyclohexane 0.01 0.28
n-Pentane 0.01 0.32
3-Methylpentane 0 0.33
2-Methylbutane 0.34
2,2,4-Trimethylpentane 0.17 0.40
2,2-Dimethylbutane 0.26 0.43
2,2-Dimethylpropane 0.38 0.44
Tetramethylsilane 0.62 0.62
Bis(trimethylsilyl)methane 0.66 0.66
Hexamethyldisiloxane 0.70 0.70
Source: Refs. 2, 33, and 34.
vent. The data were used to evaluate V
0
for 18 dierent liquids. Typical results of this and
other studies [50,51] are given in Table 1. Direct single-photon ionization of solvent mole-
cules is also sensitive to the value of V
0
[5255] and can, in principle, be used to determine V
0
.
Recently, laser multiphoton ionization of solutes has been used. Dening the
threshold of ionization, E
th
, can be a problem in some of these methods. A recent
multiphoton technique, utilizing femtosecond laser pulses, appears to give quite accurate
thresholds [56]. In this work, a conductivity spectrum is measured at visible wavelengths
and a sharp drop in current occurs as the mechanism changes from n-photon excitation to
(n+1)-photon excitation, where n is typically 3 to 4. The threshold is dened by tting the
current to an analytic function that denes the midpoint of this transition. E
th
is then n
times the energy at which the midpoint occurs. The thresholds are sensitive to V
0
and
could be used for determination of this quantity.
Photodetachment from anions should also be mentioned [5759]. In this case, the
threshold, E
th
V
, given by:
E
th
V
EAV
0
E
pol
5
is well dened since the electron escapes with high probability from the neutral molecule
left behind, and the photodetachment yields as a function of photon energy follow a
known power law. Thus V
0
values can be determined from such studies if values of the
electron anity, EA, are available.
Recently, V
0
has been measured in dense rare gas uids by eld ionization of
Rydberg states of solutes lying close to the continuum. In this technique, Reininger et al.
[6063] utilized synchrotron radiation and measured photocurrent spectra in the vacuum
ultraviolet (VUV) with a resolution of 7 meV. The photocurrent spectra were measured at
several applied electric elds. A eld ionization spectrum was obtained by subtracting the
spectrum at low eld from one obtained at high eld. Such spectra typically showed one
peak at threshold energies due to those high-lying states that ionized at the high voltage
but not at the low voltage. Measurements were made in argon containing CH
3
I [60] and
H
2
S [61] as solutes, and the density was varied from dilute gas to the triple point of argon.
The position of the eld ionization peak shifts as the density is changed. These shifts are
the combined eect of changes in the ion-media polarization energy and V
0
. Accurate
calculation of the former allowed the evaluation of V
0
as a function of density, utilizing
Eq. (4) above. The resulting values of V
0
are in good agreement with earlier photoelectric
and theoretical values. Furthermore, the two solutes CH
3
I and H
2
S gave very comparable
results. For argon, V
0
reaches a minimum value of 0.294 eV at a density of 12 10
21
cm
3
, which is the density at which the electron mobility is a maximum.
The solid line in Fig. 3 is a best t of Eq. (6) to the experimental data [61]. See cited
reference for values of the parameters in Eq. (6).
V
0
N a
0
a
1
Na
2
a
3
=a
4
ln cosh a
4
Na
2
6
The density dependence of V
0
in Kr was determined by eld ionization of CH
3
I
[62] and (CH
3
)
2
S [63]. Whereas previous studies found a minimum in V
0
at a density of
12 10
21
cm
3
[66], the new study indicates that the minimum is at 14.4 10
21
cm
3
(see
Fig. 3). This is very close to the density of 14.1 10
21
cm
3
at which the electron mobility
reaches a maximum in krypton [67], a result that is consistent with the deformation poten-
tial model [68] which predicts the mobility maximum to occur at a density where V
0
is a
minimum. The use of (CH
3
)
2
S permitted similar measurements of V
0
in Xe because of its
lower ionization potential. The results for Xe are also shown in Fig. 3 by the lower line,
which represents the analytical equation (6) giving the best t to the data. Parameter values,
a
n
, can be found in the reference cited.
The earliest theoretical model of the eect of a medium on the quasi-free electron
energy was proposed by Fermi [69] to explain ionization of high Rydberg states. This
model, which predicts a linear dependence on density, works well only at low densities.
Springett et al. [37] introduced the WignerSeitz model to calculate V
0
in several liquids
employing a simple electronatom pseudopotential. This model was used by Stampi and
Bennemann to calculate V
0
for liquid Ar, Kr, and Xe, except they solved the eigenvalue
problem numerically [64]. Their results for Ar, shown in Fig. 3 by the dashed line, are in
good agreement with the experiment. Several other modications to the theoretical
treatments have been proposed [65,7073] using various techniques. Simon et al. [74,75]
used a classical percolation approach to predict V
0
for Ar, Kr, and Xe. The calculations of
Plenkiewicz et al. [65], which use an accurate electronatom pseudopotential, are shown by
the dotted lines in Fig. 3. Their calculations also agree quite well with the experimental
data and nd the minima at the right densities. These newer studies are readily applicable
to molecular liquids and have been applied to CH
4
and SiH
4
[76].
Figure 3 Energy of the quasi-free state in rare gas uids as a function of density. Solid lines
represent recent results obtained by eld ionization for Ar [61], Kr, and Xe [see Eq. (6)] [63]. Recent
theoretical calculations are shown for Ar by the dashed lines [64] and for Ar, Kr, and Xe by the
dotted lines [65].
4. SOLVATED ELECTRONS
Evidence for the existence of a trapped state of the electron in some liquids comes from
several sources. For one, pulse radiolysis studies have shown that for certain alkanes, there
is a broad absorption in the infrared that can be attributed to the electron. Second, studies
of the eect of pressure on the mobility of electrons have revealed information about
cavity sizes and the role of electrostriction in the trapping process. Finally, conductivity
studies of reversible reactions of the electron have given us the energetics of the trapping
process. These latter equilibrium studies are described in detail in Sec. 5.1. Values of
DG
soln
(e) for selected liquids are given in Table 1. For many liquids, DG
soln
(e) lies below
the V
0
state making trapping energetically favorable.
Early pulse radiolysis studies of alkanes at room temperature showed that the sol-
vated electron absorption begins around 1 Am and increases with increasing wavelength to
1.6 Am for n-hexane, cyclohexane, and 2-methylbutane [77]. More complete spectra for
three liquid alkanes are shown in Fig. 4. The spectrum for methylcyclohexane at 295 K
extends to 4 Am and shows a peak at 3.25 Am [78]. At the maximum, the extinction
coecient is 2.8 10
4
M
1
cm
1
. The spectrum for 3-methyloctane at 127 K, shown in
Fig. 4, peaks around 2 Am. The peak for methylcyclohexane is also at 2 Am at lower
temperature. Recently, the absorption spectra of solvated electrons in 2-methylpentane,
3-methylpentane, cis-decalin, and methylcyclohexane glasses have been measured accu-
rately at 77 K [80]. For these alkanes, the maxima occur at 1.8 Am, where the extinction
coecient is 2.7 10
4
M
1
cm
1
.
Figure 4 Absorption spectra of solvated electrons in alkanes vs. wavelength. Solid line is for
methylcyclohexane at 295 K [78]. Dashed line is for 3-methyloctane at 127 K [79]. Dashdot line is
for 3-methylpentane at 77 K [80]. Spectra have been normalized to unity at the peaks.
The stronger absorption at lower temperatures can be attributed to several factors.
One is that the equilibrium between quasi-free and trapped electrons shifts to favor
trapped electrons as the temperature is lowered for these liquids. Another is that homo-
geneous recombination of electrons with positive ions is slower at the lower temperatures
and therefore occurs to a lesser extent during the pulse, which, for the pulse radiolysis
studies, was typically 10 to 20 nsec. The rate constant, k
r
, for electron recombination with
positive ions, in most nonpolar liquids, is given by:
k
r

4pel
D
e
1:09 10
15
l
e
=e M
1
sec
1
for l
e
in cm
2
Vs

7
This equation is suciently valid that it is considered to be a law of electron dynamics.
Exceptions exist only for very high values of l
D
(see Chap. 10).
It is important to consider the magnitude of the recombination rate in studies of this
type. For methane, k
r
is 1.7 10
17
M
1
sec
1
at 93 K [81]. Thus if a concentration of ions
of 0.1 AM was formed in the pulse, the electrons would disappear with a rst half-life
of 50 psec. For 2,2,4-trimethylpentane, k
r
is 3.6 10
15
M
1
sec
1
and for a similar con-
centration of electrons, the recombination lifetime would be a few nanoseconds. Where the
electron mobility is lower, the recombination rate is slower. For methylcyclohexane,
where l
e
= 0.07 cm
2
/Vs [18], k
r
is 4 10
13
M
1
sec
1
and the rst half-life should be about
250 nsec.
Electrons have not been detected by optical absorption in alkanes in which the
mobility is greater than 10 cm
2
/Vs. For example, Gillis et al. [82] report seeing no infrared
absorption in pulse-irradiated liquid methane at 93 K. This is not surprising since the
electron mobility in methane is 500 cm
2
/Vs [81] and trapping does not occur. Geminately
recombining electrons have, however, been detected by IR absorption in 2,2,4-trimethyl-
pentane in a subpicosecond laser pulse experiment [83]. The drift mobility in this alkane is
6.5 cm
2
/Vs, and the quasi-free mobility, as measured by the Hall mobility, is 22 cm
2
/Vs
(see Sec. 6). Thus the electron is trapped two-thirds of the time.
The nature of the absorption spectra has been discussed by several authors
[78,80,84,85]. Since the trapped state is not far below the conduction band, it is at least
reasonable to consider that the infrared spectrum is a bound-free transition. In the study
of alkane glasses at 77 K, mentioned earlier [80], the cross sections near threshold were
found to t the Wigner [86] power law. This supports the idea that the spectra are due to a
transition from a bound S-state to a continuum P-state. The threshold binding energy at
77 K was found to be 0.48 eV. From an analysis of the spectral distribution, the authors
obtained ground state properties of the trapped electron. The experimental spectrum
matched that derived from a simple spherical well model, suggesting that the electron
resides in a cavity of radius 0.35 nm. Other studies have arrived at a similar value for the
radius. For example, Ichikawa and Yoshida [84] obtained 0.36 nm for 3-methylpentane
glass based on a model that included a short-range repulsive contribution and an
attractive, Born-like, medium polarization. An electron spin resonance study of solvated
electrons in deuterated 3-methylpentane glasses indicated that there were an average of
three molecules in the rst solvation shell. A combination of spin-echo and second-
moment analysis gave electron to proton distances from 0.35 to 0.43 nm [87]. These studies
have provided considerable insight into the nature of the trapped state and are consistent
with the transport studies discussed below.
Studies of the eect of pressure on l
D
in a series of 10 hydrocarbons revealed more
information about the trapped state [34]. The pressure data led to the conclusion that the
partial molar volume of the electron, V
e
, is small but may be either positive or negative.
Values range from +22 cm
3
/mol for m-xylene to 27 cm
3
/mol for 1-pentene. This depends
on the relative magnitude of two large volume terms that make up V
e
. One is the cavity
volume, a positive term, and the other is the electrostriction of the solvent around the
trapped electron. Whereas the electrostriction term varies considerably depending on the
compressibility of the solvent, the cavity volume does not change much and the average
value for the hydrocarbons is 96 cm
3
/mol, corresponding to a cavity radius of 0.34 nm.
Thus from pulse radiolysis, mobility measurements, and electron reaction studies, we
have information on the absorption spectra, the cavity volume, and the energy of the
trapped or solvated state. The nature of this state seems to be an electron that is localized
in a cavity in the liquid.
5. REACTIONS OF ELECTRONS
Electron attachment to solutes in nonpolar liquids has been studied by such techniques as
pulse radiolysis, pulse conductivity, microwave absorption, and ash (laser) photolysis. A
considerable amount of data is now available on how rates depend on temperature,
pressure, and other factors. Although further work is needed, some recent experimental
and theoretical studies have provided new insight into the mechanism of these reactions.
To begin, we consider those reactions that show reversible attachmentdetachment
equilibria and therefore provide both free energy and volume change information.
5.1. Electron Equilibria
Electron equilibria of the type:
e
solute
k
d
!
k
a
solute
8
have been observed for solutes that do not dissociate on attachment and have gas phase
electron anities (EA) between 1.15 eV (benzene) [88,89] and 0.3 eV (phenanthrene) [90].
Application of high pressure facilitated the studies for solutes of very negative electron
anities like toluene, benzene, and butadiene. Equilibrium constants, K
eq
, have been eval-
uated by conductivity methods from changes in electron mobility and from determination
of both the attachment rate constants, k
a
, and the detachment rate constants, k
d
. Values
of DG
r
for various solutes are shown in Fig. 5 for tetramethylsilane, 2,2,4-trimethylpentane,
n-hexane, and supercritical ethane as solvents. It has been shown that DG
r
depends on the
polarization energy of the product anion, E
pol
(S
), and the solvation energy of the electron

DG
s
(e) according to:
DG
r
l DG
o
r
g E
pol
S
DG
s
e 9
where DG
o
r
( g) is derived from the electron anity DG
o
r
( g) = EATDS
r
( g). For all the
reactions, DG
o
r
is lower in 2,2,4-trimethylpentane than in tetramethylpentane (TMS) partly
because DG
s
(e) is higher in the former solvent and also because the dielectric constant is
higher in 2,2,4-trimethypentane, which makes the value of the solvation energy lower. The
further lowering of DG
r
for these reactions in n-hexane is due largely to the even higher value
of DG
s
(e) in this solvent.
Equilibria of this type have been used to determine the ground state of the electron in
liquids [100]. Some of the values of DG
s
(e) given in Table 1 were evaluated this way. The
reaction of the electron with CO
2
was used to measure DG
s
(e) for hexamethyldisiloxane
and bis(trimethylsilyl)methane. The electron mobility in these liquids is unusually high,
and V
0
is therefore expected to be the same as DG
s
(e). For hexamethyldisiloxane, DG
s
(e)
was found to be 0.70 eV and that for bis(trimethylsilyl)methane, it was found to be
0.66 eV (see Table 1).
These equilibrium reactions occur with large decreases in both volume and entropy.
Volume changes range from 80 to 300 cm
3
/mol depending on the solute and pressure.
These volume changes, DV
r
, are associated with the electrostriction of the solvent around
the product anion, V
el
(ion), and, to some extent, with a contribution of the partial molar
volume of the electron, V(e). Thus:
DV
r
V
el
ion V e 10
Values of V(e) are small compared to the overall volume changes (see Sec. 4). However,
magnitudes of DV
r
were found to be much larger than could be accounted for using the
classical expression for V
el
(ion) [101]:
V
el
ion e
2
=2R
ion

1=e
2

de=dP 11
To account for the dierence between experiment and theory, Schwarz suggested that
electrostriction includes the formation of a glassy shell of 7 to 9 solvent molecules around
the ion [102]. This phase transition provides a substantial density increase, and the
observed volume changes can then be accounted for.
These attachmentdetachment equilibria [Eq. (8)] shift to the right with increasing
pressure and to the left with increasing temperature. Thus the free energies decrease with
pressure and increase with temperature. These eects are related to the solvent compres-
Figure 5 Free energies for attachment to solutes: MeStmethylstyrene, Stystyrene, Bph
biphenyl, CO
2
, Pyrpyrimidine, Tphtriphenylene, Dfbp-diuorobenzene, Toltoluene, But
1,3-butadiene, Pyzpyrazine; in TMS, 2,2,4-trimethylpentane, and n-hexane at 298 K and in
supercritical ethane at 310 K. (From Refs. 9099.)
sibility, which increases with pressure and decreases with temperature. The entropy contri-
bution is less at high pressure but increases with temperature. Because both entropy and
volume changes are due to electrostriction of the solvent, these quantities are related by:
DS
el
ion a=v
T
DV
el
ion 12
where a is the coecient of thermal expansion and v
T
is the isothermal compressibility.
Electron attachment equilibria have also been observed in supercritical ethane. The
equilibrium constants are generally smaller than in liquids and consequently DG
r
is higher.
Thus, as shown in Fig. 5, DG
r
for attachment to CO
2
is higher in ethane at all pressures
than in either TMS or 2,2,4-trimethylpentane liquids. This is mainly a consequence of the
lower density of the solvent that results in less polarization energy for the anion. However,
the continuum model of Born is no longer correct for evaluating the polarization energy
because of the signicant density augmentation around the ions in supercritical nonpolar
uids. Instead, a compressible continuum model that takes this eect into account must be
used [99,103]. In the case of a supercritical solvent like ethane, the free energy of
attachment to a solute changes rapidly with pressure, particularly near critical densities
where the compressibility of the uid changes rapidly. Thus, as the pressure increases, the
values of DG
r
for attachment to CO
2
, pyrimidine, and pyrazine decrease. The equilibria in
supercritical ethane could only be observed over the pressure ranges indicated in the gure
for these solutes.
The volume changes, DV
r
, for attachment to solutes in supercritical ethane can be
extremely large and they are always negative. For pyrazine as a solute, values of DV
r
range
from 1.0 to 45 L/mol, depending on temperature and pressure. The largest changes are
found at the densities where the compressibility is the largest at each temperature. These
changes are mostly due to electrostriction of the solvent around the ion formed and are
predicted quite well by the compressible continuum model. Generally, the density
augmentation around an ion in a supercritical uid extends to a radial distance of 1 nm.
5.2. Attachment Rates
In nonpolar liquids, bimolecular electron attachment rate constants, k
a
, are much larger
than those for conventional reactions of ions or radicals. This is, in part, related to the
high mobility of electrons in these liquids; but various other factors, like V
0
, the kinetic
energy of the electron, and dipole moment of the solute, are important as well. These and
other factors are examined below; the dependence of k
a
on the energy gap, DG
r
, in
representative liquids is also shown and discussed.
It is natural to conclude that the high rate constants for electron attachment
reactions in nonpolar liquids are associated with the high mobility of electrons. Early
studies [96,104,105] of attachment to biphenyl and SF
6
emphasized the dependence of k
a
on mobility. This relationship is apparent if the expression for the rate constant for a
diusion-controlled reaction:
k
D
4pR
e
D
e
13
is combined with the Einstein relation:
D
e
l
D
k
B
T=e 14
then:
k
D
4pR
e
l
D
k
B
T=e 15
In the solvents ethane, propane, and hexane, a reaction radius, R
e
, of 1.4 nm was found for
attachment to SF
6
. This is close to the theoretical maximum radius for electron attach-
ment in the gas phase [106].
Modern theory suggests that rates of electron transfer reactions depend on the poten-
tial energy dierence [107]. For electron attachment reactions in solution, that dierence
is given by the dierence in energy of reactants, in this case, the electron plus solute, and the
product anion [see Eq. (9)]. Since this theory works so well for electron transfer, it is inter-
esting to examine the dependence of rates on DG
r
(l ) for electron attachment reactions; such
a plot for cyclohexane as solvent is shown by Fig. 6. For one of the solutes, diuoroben-
zene, DG
r
(l ) is known fromequilibriumstudies. For the other solutes, DG
r
(l ) was calculated
using Eq. (9). Values of rate constants and electron anities are fromreferences given in the
gure legend. The continuum model of Born:
E
pol
S

e
2
2R
S
1
1
e

16
was used to calculate E
pol
(S
), where the radius of the anion, R

S
, was calculated from the
molar volume of the solute. Many of the rates for cyclohexane are close to 3 10
12
M
1
sec
1
(dotted line in Fig. 6). Since the room temperature electron mobility in cyclohexane
is 0.24 cm
2
/Vs [19], this rate corresponds to a reaction radius of 0.7 nm, assuming that
Eq. (15) applies. The lack of dependence on the exothermicity, DG
r
(l ), for most of the
Figure 6 Rate constants for electron attachment to solutes in cyclohexane at 295 K. Solutes are:
1CCl
4
, 2p-dinitrobenzene, 3benzoquinone, 4o-dinitrobenzene, 5nitrobenzene, 6O
2
, 7
peruoromethylcyclohexane, 8pyrene, 9anthracene, 10biphenyl, 11naphthalene, 12CO
2
,
13p-diuorobenzene, 14ethylbromide. Dotted line indicates calculated diusion rate. References
for rate data: [19,108111]; references for electron anities: [112115].
reactions included in Fig 6 indicates that the rate is determined by the rate of diusion of
the electron to the solute.
A plot of the attachment rate in cyclohexane vs. simply the electron anity of the
solute, shown in a paper by Christophorou [116], is similar to Fig. 6 in appearance.
Christophorou concluded that for solutes with EA>0, k
a
is close to the diusion-
controlled rate. The similarity in plots is not surprising since for many of the larger solute
molecules, the polarization energy is nearly the same and thus changes in DG
r
(l ) are
proportional to changes in EA. Christophorou suggests that the rate constant drops o to
very low values when EA<0.9 eV.
Some reactants have rate constants higher than 310
12
M
1
sec
1
; examples are
nitrobenzene and o-dinitrobenzene. These two compounds have large dipole moments of
4.1 and 6.1 Debye, respectively, and it has been shown [110] that the rate constants in
cyclohexane increase with dipole moment because the reaction radius increases. That
dependence is given by [117]:
R
1
e

Z
l
r
c
exp Ur=k
B
T
r
2
dr 17
where U(r) is a function of the dipole moment and r
c
is the hard-core radius of the reactant
pair. Diusion rates calculated with Eq. (15) agree with the experimental values for a series
of nitrobenzenes when Eq. (17) is used to calculate R
e
[110].
Many of these attachment reactions are also diusion-controlled in other solvents of
low electron mobility like, for example, n-hexane. It has been suggested that this is the case
for all solvents for which l
D
<1 cm
2
/Vs [118]. For this to be true, the rate constant k
a
should scale as the mobility. For hexane, the rate constants for attachment to solutes like
biphenyl, naphthalene, and diuorobenzene are close to 1 10
12
M
1
sec
1
or one-third
the value in cyclohexane. The mobility in n-hexane is approximately one-third that in
cyclohexane [2]; thus k
a
scales with l
D
for these two solvents.
An interesting example of a diusion-controlled reaction is electron attachment to
SF
6
. Early studies showed that in n-alkanes, k
a
increases linearly with l
e
over a wide range
of mobilities from 10
3
to 1 cm
2
/Vs [119]. Another study of the eect of electric eld (E)
showed that in ethane and propane, k
a
is independent of E up to approximately 90 kV/cm,
but increases at higher elds [105]. This eld is also the onset of the supralinear eld
dependence of the electron mobility [120]. Thus over a wide range of temperature and
electric eld, the rate of attachment to SF
6
remains linearly dependent on the mobility of
the electron, l
D
, as required by Eq. (15).
Diusion is not always rate determining of course. Exceptions shown in Fig. 6 are
oxygen and peruoromethylcyclohexane for which the rate constants are below the diu-
sion rate; these are considered in more detail below. The dependence of k
a
on electron
mobility also breaks down if the mobility is >10 cm
2
/Vs. This was noted early for the
reaction of the electron with biphenyl [104,121].
Many attachment reactions have been studied in 2,2,4-trimethylpentane, a liquid for
which l
D
is 6.6 cm
2
/Vs at roomtemperature. Attachment rate constants for many solutes in
2,2,4-trimethylpentane are shown in Fig. 7 plotted vs. DG
r
(l). The dotted line shows the
diusion rate for the radius of 0.72 nm, derived for cyclohexane. In 2,2,4-trimethylpen-
tane, only a few solutes, like SF
6
, C
6
F
6
, and the metal carbonyls, come close to the diusion
rate.
The attachment rate constants for the solvent tetramethylsilane (TMS), in which the
electron mobility is 100 cm
2
/Vs, are shown in Fig. 8. The solutes include those listed in a
recent compilation by Nishikawa [2] plus pyrimidine and C
60
from recent studies [93,122].
The values of k
a
range over 4 orders of magnitude; nevertheless, some conclusions become
apparent. For large energy gaps, k
a
is close to 10
14
M
1
sec
1
, with the exception of
benzoquinone, duroquinone, and O
2
, which are special cases (see below). The diusion
rate, shown by the dotted line, was calculated using the value of R
e
= 0.72 nm suggested
for cyclohexane. None of these reactions occurs at the diusion rate in TMS. For
moderate energy gaps (DG
r
= 0.7F0.3 eV), k
a
tends to be around 10
13
M
1
sec
1
.
When DG
r
is close to zero, much lower rate constants are observed.
The value of k
a
for attachment to SF
6
given in Fig. 8 is 2.1 10
14
M
1
sec
1
. This
reaction has also been studied in other high mobility liquids including methane (l
D
= 400
cm
2
/Vs), argon (l
D
= 400 cm
2
/Vs), and xenon (l
D
= 2000 cm
2
/Vs) [127129], and the
rate constant is nearly constant at 3F1 10
14
M
1
sec
1
. This has been explained by
Warman [106] and others as due to the fact that the residence time, s
D
, of an electron
within a reaction radius, R
e
, is short compared to the attachment time, s
A
. Thus rate
constants would be expected to fall o with increasing mobility according to the equation:
k
a

4pR
e
D
1 s
A
=s
D
18
At high-enough mobility, since s
D
is R
2
e
/2D, k
a
reaches a constant value of 2pR
3
e
/s
A
i3
10
14
M
1
sec
1
, which explains the near constant rate for attachment to SF
6
observed in
liquids of high mobility.
Figure 7 Rate constants for electron attachment to solutes in 2,2,4-trimethylpentane at 295 K. For
solutes numbered 114, see legend to Fig. 6. Other solutes: 15C
60
, 16SF
6
, 17C
6
F
6
, 18
W(CO)
6
, 19Cr(CO)
6
, 20perylene, 21Mo(CO)
6
, 22t-stilbene, 23benzperylene, 24cor-
onene, 25pyrazine, 26pyrimidine, 27styrene, 28a-methylstyrene. Dotted line is calculated
diusion rate. References for rate data: [19,58,108,109,122124]; references for electron anities:
[112115].
Figs. 7 and 8 show that the rate constants are mostly below the diusion limit. Some
rates are a few orders of magnitude lower, and these reactions have been interpreted as
dependent on the energy gap. Attachment to O
2
is a case in point [123]. Like many of
these reactions, this is a nondissociative attachment reaction. As pointed out by Henglein
[130,131], attachment to O
2
is most favorable when the energy gap is small. As can be
seen in Figs. 68, DG
r
is between 2.6 and 2.0 eV for these solvents and thus the
reaction is unfavorable at room temperature. Any decrease in the gap would be expected
to increase the rate. The positive activation energy of approximately 2 kcal/mol for this
reaction in most solvents can be accounted for in this way. As the temperature increases,
the density decreases causing the energy level of the electron to decrease and the value of
E
pol
(O
2
) to increase thus narrowing the energy gap. The eect of increasing pressure on
this reaction is of interest since increasing pressure causes the density to increase, causing
the energy levels of the electron to increase and the value of E
pol
(O
2
) to decrease. Thus
the energy gap increases with increasing pressure. Preliminary studies show that the rate
of attachment to O
2
in n-pentane as solvent decreases a factor of 2 in 1 kbar [132]. The
attachment rate to O
2
has also been studied in liquid argon and xenon [127]. The rate
decreases with increasing eld or, since the eld increases the average electron energy, the
Figure 8 Rate constants for electron attachment to solutes in tetramethylsilane at 295 K. For
solutes numbered 128, see legends to Figs. 6 and 7. Other solutes: 29duroquinone, 30CH
3
I,
31cycloC
4
F
4
, 32C
2
HCl
3
, 33phenanthrene. Dotted line is calculated diusion rate. References
for rate data: [18,19,58,90,93,122,123,125,126]; references for electron anities: [112115].
rate decreases as the kinetic energy of the electrons increases. Thus at higher elds, there
is more energy available for the reaction and the rate slows down.
There is a class of solutes, including ethylbromide, N
2
O, C
2
HCl
3
, and certain
uoroalkanes, that shows negative activation energies for attachment in liquids like
TMS and neopentane [19,123]. For ethylbromide, the rate constant of electron attachment
in TMS is 4.2 10
10
at 23jC. This is point 14 in Fig. 8. Lowering the temperature causes
the energy level of the electron, V
0
, to increase and the polarization energy of the anion
E
pol
(S
) to decrease. Thus lowering the temperature increases the energy gap between the
electron energy level and the energy of the ion in solution and the rate increases. For
neopentane as solvent, the eect is similar except that the electron energy level is higher
making the gap larger, and, at 24jC, k
a
is 3.4 10
11
M
1
sec
1
, an order of magnitude
larger than in TMS. The rate reaches a maximum in 2,2,4-trimethylpentane where k
a
is
6.3 10
12
M
1
sec
1
at 23jC (point 14 in Fig. 7) because the electron level is even higher.
Thus the rate increases as the energy gap increases. In the gas phase, this reaction shows a
maximum in the attachment rate for an electron energy of 0.76 eV [133]. This value was
used for DG
r
( g) in calculating DG
r
(l). In TMS, DG
r
(l) turns out to be +0.32 eV, or this
vertical attachment reaction is unfavorable. In 2,2,4-TMP, DG
r
(l) is close to zero or, in
terms of the electron redox level picture of Henglein [134], the occupied donor level
(electron in the solvent) matches the unoccupied acceptor level (ethyl bromide). But the
rate constant is less in cyclohexane, 2 10
12
M
1
sec
1
at 23jC, where the electron level is
even higher. This is explained by the fact that the reaction is limited by the diusion rate,
which should be somewhat less than the line in Fig. 6 because of a smaller reaction radius
for this solute.
The explanation of the negative activation energies for attachment to N
2
O, C
2
HCl
3
[19], and peruorocyclobutane [123] in TMS is similar to that for ethylbromide above.
These molecules exhibit maxima for electron attachment in the gas phase at 2.2 eV [135],
0.4 eV [136], and 0.35 eV [137], respectively. Thus rates are expected to increase as the
energy gap increases. However, in 2,2,4-TMP and n-hexane, the attachment rates show
normal Arrhenius behavior. For these solvents, the ratio k
a
/l
D
is constant over a range of
temperatures indicating that the reaction becomes diusion-limited as was the case for
ethylbromide in cyclohexane. Other peruoroalkanes like n-C
5
F
12
and n-C
6
F
14
are
reported to show maxima as is seen for cyclo-C
4
F
8
[138].
Carbon dioxide reacts in a manner similar to the solutes discussed above in that as
the energy gap increases, the rate of attachment increases. However, unlike the other
solutes, this reaction is reversible in solution and the equilibrium:
e
CO
2
VCO
2
19
has been studied in several nonpolar liquids as well as in supercritical ethane. Thus not
only the attachment rates, k
a
, have been measured, but also values of the free energy of
reaction, DG
r
, are available. The rate constants, k
a
, for this reaction, obtained at various
temperatures and pressures in several uids: TMS, 2,2,4-trimethylpentane, dimethylbu-
tane, and supercritical ethane [126,139], are plotted in Fig. 9. In liquids, the rate constant is
independent of temperature at any pressure but increases with pressure. The increase in
rate with pressure can be explained by the increase in electron energy level [39] and the
increase in stability of the ion with pressure that causes the energy gap to increase. As
shown in Fig. 9, log k
a
is linearly dependent on DG
r
and k
a
increases about 3 orders of
magnitude as the energy gap increases by 0.4 eV.
The reaction of electrons with p-benzoquinone is an unusual case. A conductivity
study showed that the reaction is slow at room temperature in TMS and neopentane and
the activation energies are negative [140]. The energy gaps are large: DG
r
(l) is 2.3 eV
in TMS and 2.44 eV in neopentane, indicating possible inverted behavior. However,
in 2,2,4-TMP, DG
r
(l) is even lower, 2.58 eV, and the rate of attachment is fast. In
cyclohexane, n-pentane, and n-hexane, where the electron levels are high, the reaction
appears to be diusion-limited. The results were explained by assuming an equilibrium
with an excited state of the anion:
e
benzoquinone Vbenzoquinone
* 20
benzoquinone
* Ybenzoquinone
21
The excited state lies 2.07 eV above the ground state; thus there is sucient energy
available in all solvents to reach this state. The kinetic analysis indicated that the
attachment rate is fast in all solvents. In TMS, neopentane, and 2,2,4,4-tetramethylpen-
tane, the energy levels of the electron are low enough that the reverse reaction, autodetach-
ment from the excited anion, occurs with small activation energy.
Recently, the excited state of benzoquinone anion was detected both by absorption
and uorescence [141]. The lifetime of the excited state in 2,2,4-trimethylpentane is c120
nsec or k
21
= 8 10
6
sec
1
. If it is assumed that the lifetime is similar in the other
nonpolar solvents, then the results of the two studies may be combined to evaluate the
detachment rate from the excited anion. At room temperature, this calculation gives
k
20
= 6 10
8
sec
1
in TMS; thus detachment readily competes with deactivation of
the excited state of benzoquinone anion. The latter process includes internal conversion as
well as uorescence. In 2,2,4,4-tetramethylpentane, where the activation energy for detach-
ment is 0.41 eV, k
20
is 4 10
6
sec
1
and some autodetachment occurs along with uo-
rescence. In solvents like n-pentane, n-hexane, and cyclohexane, the activation energies for
Figure 9 Rate constants for electron attachment to CO
2
vs. the free energy of reaction in dierent
uids: w2,2,4-trimethylpentane [126], .2,2-dimethylbutane [139], oTMS [126], nsuper-
critical ethane [99].
detachment are much higher because the electron energy levels are higher, and the reaction
proceeds directly to benzoquinone anion at the diusion rate.
For attachment to CO
2
, the rate constant clearly shows a dependence on DG
r
(l ).
However, for attachment to other solutes like aromatics, the dependence on DG
r
(l ) is not
yet clear. Questions remain like what is the role of reorganization energy, which can be
large even in nonpolar solvents [142]; it was pointed out earlier that there is considerable
density augmentation around the negative ions formed in attachment reactions. For
solvents like TMS, rates maximize for values of DG
r
(l ) near 0.7 eV; what rate is to be
expected for large values of DG
r
(l )? Is the high rate observed for C
60
typical or the low
rate for quinones more typical? Further study is needed to resolve these questions.
6. TRANSPORT PROPERTIES
6.1. Quasi-Free Mobility
The drift mobility of electrons in nonpolar liquids ranges from high values such as that for
liquid xenon of 2000 cm
2
/Vs to low values like that for tetradecane of 0.02 cm
2
/Vs. It has
often been suggested that the mobility is high for symmetrical molecules and low for
straight chain molecules like n-alkanes. Inspection of Table 2 shows that liquids with
symmetrical molecules are indeed at the top of the list. However, other less symmetrical
molecules like bis-trimethylsilylmethane and 2,2,4,4-tetramethylpentane also show high
drift mobility. A more important factor may be the existence of many methyl groups in the
molecule. In any case, for liquids for which l
D
>10 cm
2
/Vs, the electron is considered to
be quasi-free. This is supported by the Hall mobility studies, as discussed below.
The mobility of quasi-free electrons has recently been explained by the deformation
potential theory. Originally from solid-state physics, this theory was applied by Basak and
Cohen [68] to liquid argon. The theory assumes that scattering occurs when the electron
encounters a change or uctuation in the local density which results in a potential change.
The potential is assumed to be given in terms of dV
0
/dN, d
2
V
0
/dN
2
, etc. The formula they
derived for the mobility is:
l
D

2et
4

2p
p
m
e
=m*
5=2
3m
5=2
e
k
B
T
1=2
k
B
N
2
V
V2
0
Tv
T
V
W2
0
b=k
B
. . .

; 22
where v
T
is the isothermal compressibility and m* is the eective mass of the electron. A
similar expression was derived by Berlin et al. [144]. Equation (22) was later shown to
account for many of the features of the density dependence of the mobility in Ar, Kr, and
Xe [66]. Namely, it predicts a minimum in the mobility near the critical density and it
correctly predicts a maximum in the mobility at the density at which V
0
is a minimum, i.e.,
when dV
0
/dN = 0 (compare Figs. 3 and 10). Scattering in these uids is weakest at this
density. At higher densities, a decrease in mobility is predicted as is observed experimen-
tally. Although the general features of the experimental mobility are reproduced, the
predicted values of l
D
around the minimum near N
C
are much too small largely because
v
T
for the uids are very large in this region. Arguing that electronmedium interactions
are relatively short-ranged, Nishikawa [147] suggested that v
T
be replaced by the adiabatic
compressibility. This greatly improved the agreement at these densities for Ar.
Since these papers were published, accurate values of V
0
in argon have been obtained
by the eld ionization technique [60,61] as described in Sec. 3. Also, the eective mass, m*,
of the electron in argon is now available from theory [148] (see Sec. 6.5). Previous workers
had taken m* = m
e
. As a test of Eq. (22), the mobility in argon was recalculated here using
these new data. The adiabatic compressibility was used and the value of b was obtained by
making both sides of Eq. (22) equal at the density at which V
0
is a minimum. Fig. 10 shows
that this calculated mobility compares well with the experimental data of Jahnke et al.
[145]. This theory has also been shown to predict quite well the density dependence of the
mobility in xenon [149].
This theory has also been used to predict mobility for molecular liquids. Neopentane
and TMS are liquids that exhibit maxima in the electron mobility at intermediate densities
[46]. These maxima occur at the same densities at which V
0
minimizes, in accordance with
the BasakCohen theory. The drift mobility in TMS has been measured as a function of
pressure to 2500 bar [150]. The observed relative experimental changes of mobility with
pressure are predicted quite well by the BasakCohen theory; however, the predicted value
of l
D
is 2.5 times the experimental value at 1 bar and 295 K. In this calculation, the
authors used v
T
to evaluate the mobility. This is reasonable in this case since for liquids,
there is little dierence between the adiabatic and isothermal compressibilities. A similar
calculation for neopentane showed that the BasakCohen theory predicted the Hall
mobility of the electron quite well for temperatures between 295 and 400 K [151]. Itoh
Table 2 Free Ion Yields and Mobilities at 293295 K
No. Liquid G
(electrons/100 eV) l
D
(cm
2
/Vs)
1 Tetramethylsilane 0.7 100
2 Tetramethylgermane 0.63 90
3 Neopentane 1.1 69
4 Bis-trimethylsilylmethane 0.5 63
5 Bis-trimethylsilylethane 0.41 47
6 Ethane 0.94 37
7 2,2,4,4-Tetramethylpentane 0.74 26
8 Hexamethyldisiloxane 0.30 22
9 Hexamethyldisilane 0.33 20
10 2,2-Dimethylbutane 0.58 12
11 2,2,5,5-Tetramethylhexane 0.67 12
12 2,2,4-Trimethylpentane 0.33 6.6
13 2,2,3,3-Tetramethylpentane 0.42 5.2
14 Polydimethylsiloxane 0.24 4.6
15 Propane 0.19 2.6
16 Cyclopentane 0.16 1.1
17 2-Methylbutane 0.17 0.93
18 3,3-Diethylpentane 0.23 0.76
19 2-Methylpentane 0.15 0.29
20 Cyclohexane 0.15 0.24
21 3-Methylpentane 0.15 0.20
22 n-Pentane 0.15 0.14
23 n-Hexane 0.13 0.074
24 Benzene 0.054 0.13
25 Toluene 0.051 0.08
26 Methylcyclohexane 0.12 0.068
et al. [152] extended the theory to mixtures taking concentration uctuations into account,
but found that the data for TMSneopentane mixtures were best t if only density
uctuations were considered.
Other theories have been proposed in recent years to account for the mobility of
quasi-free electrons. Borghesani et al. [153] studied the eld dependence of the mobility in
ArKr and ArXe mixtures and found that the results disagreed with the deformation
potential model. Instead, the results could be described by a gas-kinetic model if
concentration-dependent scattering cross sections were used. Atrazhev and Iakubov
[154] used pseudopotential theory and similarly derived density-dependent scattering
lengths, which varied from negative values at low density to positive values at high
density. Their theory qualitatively describes the density dependence of the mobility in Ar,
Kr, and Xe. Naveh and Laikhtman [155] introduced scattering from longitudinal acoustic
phonons into the deformation potential framework. Their theory gave excellent agreement
with experimental results for Ar for densities from 0.8 to 11.2 10
21
cm
3
. A dierent
approach was used by Hsu and Chandler [146] who used Feynmans polaron theory [156]
for the mobility and a pseudopotential consisting of attractive and repulsive parts. These
two terms counteract at some intermediate density and result in a peak in the mobility.
Their calculation for Ar is shown as dashed line in Fig. 10.
Figure 10 Drift mobility in argon as a function of density. .: Experimental results at 55 bar
[145]. : Calculation using modied BasakCohen (see text). - - -: Calculation by Hsu and Chandler
[146].
The deformation potential model seems to provide a suitable framework to under-
stand the quasi-free electron mobility in nonpolar liquids. Already several extensions or
modications on this theory have been proposed, and the dependence on temperature and
pressure seems to be adequately explained. However, several authors have taken dierent
approaches to the problem showing that a consensus in our understanding has not yet
been reached.
6.2. Trapped State Transport
For many nonpolar liquids, the electron drift mobility is less than 10 cm
2
/Vs, too low to be
accounted for in terms of a scattering mechanism. In these liquids, electrons are trapped as
discussed in Sec. 4. Considerable evidence now supports the idea of a two-state model in
which equilibrium exists between the trapped and quasi-free states:
e
qf
V e
tr
23
The magnitude of the mobility then depends on the value of the quasi-free mobility in such
liquids multiplied by the fraction of time the electron is quasi-free since the trapped
electron is relatively immobile. Thus:
l
D
l
qf
e
qf

e
qf

e
tr

l
qf
1
1 K
23
24
This equilibrium depends on many factors like V
0
, DG
soln
(e
), temperature, and pressure.

Dierences in these and other factors are presumed to account for the wide range of
mobilities observed (see Table 2).
Studies of the eect of pressure on l
D
for nonpolar liquids provided support for
the two-state model. Pressure aects the position of the equilibrium [Eq. (23)] because of
the volume change associated with trapping of the electron, DV
tr
. These volume changes
were deduced from changes in l
D
with pressure. For n-alkanes [157] as well as some al-
kenes [158], the mobility decreases with pressure, as shown in Fig. 11 for n-hexane and 1-
pentene.
These changes in l
D
led to values of DV
tr
equal to 22 and 27 cm
3
/mol for n-
hexane and 1-pentene, respectively. The negative volume changes are due to the role of
electrostriction [160] of the solvent around the trapped electron, and the electrostriction
volume, V
el
, is a function of the isothermal compressibility v
T
of the liquid.
For certain liquids like cyclohexene [158], o-xylene, and m-xylene [159], the mobility
increases with increasing pressure (see Fig. 11). These results provided the key to under-
stand the two-state model of electron transport. In terms of the model, DV
tr
is positive; for
example, for o-xylene, DV
tr
is +21 cm
3
/mol. Since electrostriction can only contribute a
negative term, it follows that there must be a positive volume term which is the cavity
volume, V
cav
(e). The observed volume changes, DV
tr
, are the volume changes for reaction
(23). These can be identied with the partial molar volume, V
e
, of the trapped electron
since the partial molar volume of the quasi-free electron, which does not perturb the
liquid, is assumed to be zero. Then the partial molar volume is taken to be the sum of two
terms, the cavity volume and the volume of electrostriction of the trapped electron:
DV
tr
iV
e
V
cav
e V
el
e 25
Whether V
e
is positive or negative depends on the relative value of the two terms in Eq.
(25). Ten hydrocarbons were studied and the cavity volume term was found to be rela-
tively constant at 96 F 18 cm
3
/mol. The electrostriction term varies, however, with the
compressibility of the liquid. The compressibilities of the xylenes are approximately one-
third that for 1-pentene. Thus the cavity volume term dominates for the xylenes and DV
tr
is positive. The V
el
term dominates for 1-pentene and n-alkanes and DV
tr
is negative.
The main experimental eects are accounted for with this model. Some approxima-
tions have been made; a higher-level calculation is needed which takes into account the
fact that the charge distribution of the trapped electron may extend outside the cavity into
the liquid. A signicant unknown is the value of the quasi-free mobility in low mobility
liquids. In principle, Hall mobility measurements (see Sec. 6.3) could provide an answer
but so far have not. Berlin et al. [144] estimated a value of l
qf
= 27 cm
2
/Vs for hexane.
Recently, terahertz (THz) time-domain spectroscopy has been utilized which is sensitive to
the transport of quasi-free electrons [161]. For hexane, this technique gave a value of l
qf
=
470 cm
2
/Vs. Mozumder [162] introduced the modication that motion of the electron in
the quasi-free state may be in part ballistic; that is, there is very little scattering of the
electron while in the quasi-free state.
Thus considerable support exists to support the two-state model of electron transport.
The magnitude of the mobility is dependent on many factors including V
0
, l
qf
, DG
soln
(e),
temperature, pressure, and other factors. Presumably, dierences in these factors can
Figure 11 Relative drift mobility as a function of pressure for low mobility liquids. Mobility at 1
bar in parenthesis. o: 1-pentene (0.048) [158]; 5: n-hexane (0.071) [19,150]; w: 3-methylpentane
(0.22) [2,157]; D: cyclopentane (1.02) [157]; z: cyclohexene (1.39) [158]; x: m-xylene (0.08) [159]; .:
o-xylene (0.019) [159].
explain the wide range of mobilities observed for nonpolar liquids. For example, Mozumder
[163] has recently related l
D
to G
for a series of hydrocarbons through the thermalization

distance. The fact that the mobility of trans-2-butene is approximately 100 times lower than
that of cis-2-butene (2.2 cm
2
/Vs) [164] is still quite surprising.
6.3. Hall Mobility
Measurements of the Hall mobility of electrons in nonpolar liquids are few in number, but
those that have been made provide information about the transport processes that is not
available from drift measurements alone. The Hall mobility, l
H
, is obtained by measuring
the deection of electrons by a magnetic eld while they are drifting in an electric eld.
Since the deection occurs only while the electrons are quasi-free, l
H
is a measure of l
qf
.
Measurements of l
H
that have been done are for liquids of high drift mobility. The results
for liquid argon [165] and xenon [166] show that l
H
is approximately equal to l
D
near the
respective triple points. The results for TMS indicate that the ratio l
H
/l
D
is close to unity
over a large temperature range from 295 to 437 K [167]. For neopentane, l
H
is quite
comparable to l
D
at temperatures from 293 K to 413 K; however, near the critical
temperature, 434 K, the ratio l
H
/l
D
is about 5, suggesting that there are localized states
produced by density uctuations in neopentane at this temperature [151,168]. This eect is
similar to the localization in clusters observed in xenon near the critical density (see
above). For 2,2-dimethylbutane, l
H
is 12 cm
2
/Vs, and for 2,2,4,4-tetramethylpentane, l
H
is 32 cm
2
/Vs at 293 K [169]. These values are comparable to the values of the drift mobility
for these compounds (see Table 2). For 2,2,4-trimethylpentane, l
H
is 3.5 times l
D
at room
temperature, indicating that trapping occurs in this liquid, which is consistent with the
observation of the solvated electron in this liquid (see Sec. 4).
6.4. Diffusion Coefficient
For molecular liquids, the diusion coecient of the electron can be obtained from the
mobility and the Einstein relation Eq. (14). The electrons remain thermal in such liquids,
and the temperature, T, of the liquid can be used in Eq. (14). In liquid rare gases, this is not
the case if an electric eld is applied, which causes the electrons to gain energy. The extent
of this eect was measured for liquid argon by Shibamura et al. [170]. The energy was
derived from the diusion broadening of the electron cloud during drift of the electrons in
an electric eld. Values of D
e
were derived and the energy, k
B
T, of the electrons was
calculated from Eq. (14). The electron energy was found to increase from 0.1 to 0.4 eV as
the electric eld increased from 2 to 10 kV/cm.
6.5. Effective Mass (m*)
Because of the lack of long-range order in liquids, the quasi-free electron is subjected to
multiple scattering. This is taken into account by making an eective mass approximation
in theoretical calculations of the mobility [see Eq. (22) and Sec. 3]. Previously, because of
the lack of experimental data, the eective mass was put equal to the free electron mass.
The eective mass has been evaluated [171] for some liquids from O
2
ionization cross-
section spectra [172]. This procedure gave m* =0.26m
e
for argon at 87 Kand m* =0.27m
e
for TMS, 2,2-dimethylbutane, and 2,2,4-trimethylpentane at 296 K. From exciton spectra,
Reininger et al. [173] determined m* for argon to be 0.55m
e
at the triple point. In a similar
way, Reshotko et al. [174] determined m* to be 0.28m
e
for Xe at several densities near N
t
.
Recently, the eective mass of the electron has been calculated [148] within a
WignerSeitz framework [175] for Ar, Kr, and Xe. In all three liquids, m* decreases
with increasing density. At the triple point densities, m* = 0.6m
e
in argon and m* = 0.3m
e
in xenon.
6.6. Fast Negative Ions
In some liquids, the electron is trapped as a solvent negative ion, yet transport occurs
much faster than expected for an ion. A well-documented example of this type of
electronic transport is found in liquid peruorobenzene where the electron attaches to
form C
6
F
6
[176]. Although the V

0
level is not known for this liquid, the anion is stable
because the electron anity of C
6
F
6
is 1.1 eV and the anion is further stabilized by
polarization. However, the negative ion has a mobility of 0.018 cm
2
/Vs, much greater than
that of the positive ion. Another example is the negative ion in liquid CS
2
, which has a
mobility approximately 10 times that of the positive ion [177]. In supercritical CO
2
, the
anion also has a high mobility. At 41jC, the solvent anion mobility is 0.01 cm
2
/Vs near
critical density and increases with density to 0.015 cm
2
/Vs at 0.8 g/cm
3
. This increase is
expected for a hopping mechanism since the average distance between sites decreases as
the density increases. Solute ions are reported to have a mobility of about 0.002 cm
2
/Vs at
this temperature in supercritical CO
2
[178].
Studies have shown that the electron mobility in aromatic liquids changes upon the
application of external pressure but becomes constant above 2 kbar. At low pressures, the
electron is trapped in a cavity as discussed for alkanes in Sec. 6.2. Increasing the pressure
causes the equilibria
e
A V A
26
to shift to the right. The mobility observed at high pressure is 0.06 cm
2
/Vs for toluene
[179], V0.08 cm
2
/Vs for benzene [179], and 0.06 and 0.04 cm
2
/Vs for m-xylene and o-
xylene, respectively [159]. Transport at high pressure is believed to occur by hopping:
A
A !AA
27
Hopping occurs between neighboring molecules and the activation energies are small,
from 0.12 to 0.15 eV for the hydrocarbons. Fast anions have also been suggested for liquid
SF
6
[180]. Thus several examples of this type of transport for the negative charge exist
and the mobilities are comparable. More examples of fast ions are expected to be found
in the future.
6.7. Positron Mobility
It is interesting to compare the properties of positive electrons, positrons, with the
properties of electrons in nonpolar liquids. Values of the mobility of positrons, l
+
, are
now available for a few liquids. Early measurements for l
+
in n-hexane ranged from 8.5 to
100 cm
2
/Vs [181,182]. In a recent study, the Doppler shift in energy of the 511-keV
annihilation gamma ray in an electric eld was utilized to measure the drift velocity. This
method led to l
+
= 53 cm
2
/Vs in n-hexane and 69 cm
2
/Vs in 2,2,4-trimethylpentane [183].
Interestingly, these values are comparable to the mobilities of quasi-free electrons in
nonpolar liquids.
7. APPLICATIONS
This chapter would not be complete without mentioning the applications of electrons in
nonpolar liquids. Scientists who are very interested in the properties of electrons in these
liquids are the detector physicists, working in high-energy physics, gamma ray astronomy,
cosmic radiation, or positron emission tomography [184]. Ionization chambers are used in
these elds to detect particles by the current signals induced by the excess electrons
produced. Ideal liquids for such applications would have high free ion yields, high drift
velocities, and high density. Liquid purity is important as well so that the electrons live
long enough to reach the electrode.
There are a variety of detectors currently in use to detect particles from neutrinos to
weakly interacting massive particles (WIMPS). Table 3 is a partial list of some of these
that are currently in use or under construction. As noted, some utilize multiton quantities
of liquid. The rst such detector was a sampling calorimeter containing 300 L of liquid
argon [185]. Many of the detectors in use today in high-energy physics experiments are of
this type. They are calorimeters because the particles are totally stopped within the
detector and the energy of the particles can be determined by the ionization produced in
the liquid. Heavy metal plates, each a few millimeters thick, are introduced and the
ionization is sampled in the liquid between the plates. An electromagnetic calorimeter
detects electrons and gamma rays. The latter create electronpositron pairs; these in turn
produce lower-energy gammas that create more pairs, etc. This sequence of events is called
an electromagnetic shower. The D0 detector at Femilab is an example that has been in
operation since 1991 [186]. Calorimeters that record signals from hadrons (protons,
neutrons, kaons, pions, etc.) are often incorporated in such detectors. These utilize thicker
metal plates. Calorimeters have necessarily grown as the energy of the particles in high-
energy physics experiments has increased. For example, the A Torcidal Large Hadron
Collider Apparatus (ATLAS) detector at European Center for Nuclear Research (CERN)
is a 200-kt detector. Specic details about these detectors are given in the cited references
Table 3 Ionization Detectors
Name Liquid Location Type Detects Year
D0 42,000
L Ar
Fermilab EM and hadronic
sampling
calorimeter
Electrons, photons,
and hadrons
1991
Walic TMP UA1-CERN EM sampling
calorimeter
1988
210 L
TMS
Karlsruhe Calorimeter Cosmic rays 1994
KEDR 24 t Kr Novosibirsk EM calorimeter 1996
ICARUS 600 t Ar Gran Sasso
Italy
Time projection
chamber
Neutrinos p decay 2001
ATLAS 140 t Ar CERN EM and hadron
calorimeters
Electrons,
photons, hadrons,
and Higgs boson
2007
LXeGRIT 7 L Xe Balloon Compton telescope Gamma rays 1999
DAMA/Xe-2 2 L Xe Gran Sasso Scintillator WIMPS 1998
[187]. To avoid the necessity of a cryogenic container, some calorimeters have utilized
molecular liquids like TMS [188] and 2,2,4,4-tetramethylpentane [189].
Another type of liquid detector is the time projection chamber. Examples are Imag-
ing Cosmic and Rare Underground Signals (ICARUS), a large liquid Ar detector [190],
and LXeGRIT (gamma ray imaging telescope) [191]. These detectors determine both the
energy and the direction of the incoming particle or photon [192]. Liquid xenon detectors
are usually smaller due to the high cost of xenon. For the purposes of gamma-ray as-
tronomy, the scintillation of the xenon provides a trigger for an event and the direction of
the particle is obtained by measuring the time required for electrons to drift to the collecting
electrodes. Balloon ights by E. Apriles group from Columbia have demonstrated the fea-
sibility of such gamma-ray telescopes [191].
ACKNOWLEDGMENTS
The preparation of this chapter was done at Brookhaven National Laboratory and sup-
ported under contract DE-AC02-98-CH10886 with U.S. Department of Energy and sup-
ported by its Division of Chemical Sciences, Oce of Basic Energy Sciences.
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9
Interactions of Low-Energy Electrons with
Atomic and Molecular Solids
Andrew D. Bass and Leon Sanche**
University of Sherbrooke, Sherbrooke, Quebec, Canada
1. INTRODUCTION
Low-energy electronmolecule scattering has been studied in the gas phase for over 80
years, beginning with experiments by Franck and Hertz [1] in 1914 (for a review of gaseous
electronmolecule collision processes, see Refs. 25). While such research has usually been
performed on isolated targets, more recent work (commencing around 1980) has extended
electron-scattering type measurements and theory into the condensed phase to deter-
mine the interactions of electrons with the atomic and molecular constituents of solids and
liquids, thus providing new challenges to our understanding of the basic physics of
electron scattering. Particular attention has been directed to the interactions of low-energy
electrons (LEEs), that is, electrons with kinetic energies lower than 30 eV, since these
species are implicated in a large number of phenomena and processes operating in the
condensed phase systems, from radiation damage [6] and the electronic aging of dielectrics
[7], friction induced damage to lubricants [8] and nanolithography [9], and to (potentially)
the production of O
2
in extraterrestrial water ices [10] and depletion of the ozone [11].
Low-energy electrons are of special relevance to radiobiology since high-energy
radiation interacting with condensed matter (i.e., liquids to solids) generates as the most
abundant intermediate species electrons with energies lower than 70 eV [6,12,13], within
nanoscopic volumes along ionization tracks. About four secondary electrons per 100 eV
deposited are created with a most probable energy lying below 10 eV. At these energies,
electrons have thermalization distances of the order of 110 nm [13], which eectively
dene the initial volume for energy deposition by high-energy radiation. In these volumes,
termed spurs, the highly excited atomic, molecular, and radical species ions and sec-
ondary electrons can induce nonthermal reactions within femtosecond times. A majority
of these reactive species, including those that initiate further chemical reactions, are
created by the secondary electrons. Thus to reach a comprehensive understanding of
radiation energy deposition processes in condensed matter at the nanoscopic level, it is
necessary to identify the interactions of these electrons.
* Canada Chair in the Radiation Sciences.
In the early 1990s, one of us (LS) reviewed the then available experimental data on
LEE interactions with atomic and molecular thin lms [14,15]. In the intervening years,
considerable progress has been made, and it is now appropriate to review this more recent
work. Thus in this contribution, we will largely restrict the discussion to research con-
ducted since 1990, although reference to older material will also be given. Moreover, it
should be noted that with the exception of materials of biological interest, discussion is
further limited to measurements and processes occurring in the multilayer atomic and
molecular solids. Particular attention will be paid to electron-driven processes that initiate
molecular fragmentation and/or other chemical change and to the formation of transient
negative ions (TNIs) which occur when an electron becomes temporarily bound to an
atom or molecule and which can greatly enhance scattering cross sections.
The article is organized as follows. In Sec. 2, we describe some of the basic physics of
the interactions of LEEs with isolated molecules, including an account of the DEA
process. In Sec. 3, we review experimental investigations of LEE impact on simple atomic
and molecular solids. Studies of electron impact on molecules of biological interest are
reviewed separately in Sec. 4. Finally, in Sec. 5, we consider with examples the relevance of
this work for application in areas other than radiobiology.
2. THEORETICAL BACKGROUND
Since electrons have a negligible mass compared to those of atoms and molecules, they can
exchange very little energy by momentum transfer with such particles at low velocities.
Hence to transfer considerable energy in a single event, the electron must be coupled to
a target by its electrodynamic interaction potential or by the constructive interference of
its wave function. The latter is associated primarily with the internal structure (i.e., orbital
congurations, internuclear distances, symmetry, etc.) of an atom or a molecule and, to a
lesser extent, with the geometrical arrangement of the atomic or molecular constituents of
a molecular solid or liquid. When intra-atomic and/or intramolecular constructive inter-
ference occurs, we refer to this phenomenon as the formation of an electron resonance.
Constructive and destructive interference of electron waves, delocalized over many atoms
or molecules of a solid or liquid, is known as electron diraction and is highly dependent
on the geometrical arrangement of the target and its band structure.
The electrodynamic interaction potential acting between a diatomic molecule and an
electron outside a molecule can be written as
V
l
e
r
2
P
1
!
r
!
R
Q
e
r
3
P
2
!
r
!
R
1
ae
2
2r
4

aVe
2
2r
4
P
2
!
r
!
R . . .
where r is the distance of the incident electron from the molecule and R is the internuclear
separation; l
e
is the electric dipole moment. The term containing l
e
is necessarily absent in
homonuclear diatomic molecules. The second term, involving Q
e
, the quadrupole moment,
characterizes the quadrupole interaction. These two terms are the electrostatic terms in
that they pertain to the interaction of the incident electron and the unperturbed molecule.
The next two terms involving a, the spherically symmetric, and aV, the nonspherical part of
the polarizability, are the dynamic terms. The latter involve the polarization of the
molecule by the incident electron. In Eq. (1),
!
r and
!
R are unit vectors in the directions r
and R, respectively, and P
n
are the Legendre polynomials. The parameters a, aV, l
e
, and Q
e
are functions of R. It can be seen from Eq. (1) that by estimating the magnitude of the
various terms, it may be possible to sort out the dominant scattering mechanism. For
example, the potential of Eq. (1) can be expanded around the equilibrium distance R
e
along an internuclear coordinate of the molecule as
V VR R
e
R R
e
BV
BR
R R
e
. . . 2
When only these two terms are considered and the molecule is assumed to be a harmonic
oscillator, solving the problem within the Born approximation (usually corresponding
to small momentum transfer) leads to the optical selection rule Dv = 1 for vibrational
transitions [16]. Thus within this most restrictive approximation, the electron behaves like
electromagnetic radiation. From this analysis, we can expect the electronmolecule
potential described by Eq. (2) to be responsible for the magnitude of the dierential
scattering cross sections which are large only for small scattering angles and the excitation
of the rst vibrational energy level (v = 1) from the ground state of the molecule.
Electron resonances occur when the scattered electron resides for a much longer time
than the usual scattering time in the neighborhood of a target atom or molecule. From an
atomic or molecular orbital perspective, a resonant state may be considered as a TNI
formed by an electron in which it occupies an orbital of the target. This concept leads to
the denition of two major types or categories of resonances or transient anions [17,18]. If
the additional electron occupies a previously unlled orbital of the target in its ground
state, the transitory state is referred to as a single particle resonance. The term shape res-
onance applies more specically when temporary trapping of the electron is due to the
shape of the electronmolecule potential. When the transitory anion is formed by two
electrons occupying previously unlled orbitals, the resonance is called core-excited or
may be referred to as a two-particle, one-hole state.
When an electron resonance occurs, the temporary capture of an electron at an
atomic or molecular site increases the interaction time of the electron at that site in
proportion to the resonance lifetime (s
a
f
10
16
10
13
sec) and the inverse of the electron
transfer rate. This local interaction causes a distortion of the atom or molecule which ac-
cepts the additional electron. When the electron leaves the molecule, nuclear motion is
initiated toward the initial internuclear distance, causing excitation of many overtones of
the molecule, due to the strong overlap between the nuclear wave function of the resonant
state and those of many vibrational states of the molecular ground state. On the other
hand, when s is much smaller than a typical vibrational period (s10
14
sec), the nuclei are
not signicantly displaced. In this case, overlap between the nuclear wave function of the
resonant state and that of the vibrational levels of the ground state occurs only between
the rst few energy levels. Thus for short resonance times, only the lower vibrational levels
become excited with considerable amplitude.
Dissociative electron attachment (DEA) occurs when the molecular transient anion
state is dissociative in the FranckCondon (FC) region, the localization time is of the
order of or larger than the time required for dissociation along a particular nuclear co-
ordinate, and one of the resulting fragments has positive electron anity. In this case, a
stable atomic or molecular anion is formed along with one or more neutral species.
Dissociative electron attachment usually occurs via the formation of core-excited reso-
nances since these possess suciently long lifetimes to allow for dissociation of the anion
before autoionization.
Within a local complex potential curve crossing model, the cross section for the
simple DEA reaction e AB
!
AB
!
A
B, where AB is a diatomic molecule, may be

expressed as [18]
r
DEA
E
i
r
cap
E
i
P
S
3
where P
S
represents the survival probability of the anion against autodetachment of the
electron and E
i
is the incident electron energy. The capture cross section r
cap
is given by
r
cap
E
i
k2g v
t
j j
2
C
a
C
d

4
where k is the de Broglie wavelength of the incident electron, g is a statistical factor, and v
t
is the normalized vibrational nuclear wave function. C
a
is the local energy width of the
AB
state in the FC region and C

d
is the extent of the AB
potential in the FC region. The

width of the transient anion state in the autodetaching region denes the lifetime s
a
towards autodetachment, s
a
(R) = h
J
/C
a
(R), such that the survival probability of the
temporary anion, after electron capture, is given by
P
S
exp
Z
R
c
R
e
dt
s
a
R

5
where R
e
is the bond length of the anion at energy E
i
and R
c
is that internuclear separation
beyond which autodetachment is no longer possible. If we dene an average lifetime s
a
and
let K u k
2
gjv
m
j
2
, then Eq. (3) becomes
r
DEA
E
i
K
C
a
C
d

exp
s
c
s
a
" #
6
Here s
c
(E) u jR
c
R
e
j/v where v is the average velocity of separation of the fragments A
and B upon dissociation. Hence the DEA cross section depends exponentially on the prod-
uct of the lifetime of the transient anion and the velocities of the fragments. Equation (6)
denes most of the intrinsic characteristics of the DEA process. It may be seen from this
equation that the magnitude of the DEA cross section depends on parameters which are
inuenced by the nature of the target, i.e., the attaching electron wavelength k, the
resonance lifetime s
a
, and curve crossing at R
c
.
Equation (6) denes most of the intrinsic characteristics of the DEA process. For
further information on the mechanism of transient anion formation and its eects in
isolated electronatom and electronmolecule systems, the reader is referred to the review
articles by Schulz [17] and others [7,19,20]. Information on resonance scattering from
single layer and submonolayer of molecules physisorbed or chemisorbed on conductive
surfaces can be found in the review by Palmer et al. [2123]. The present article provides
information essentially on resonances in atoms and molecules condensed onto a dielectric
surface or forming a dielectric thin lm.
3. EXPERIMENTAL STUDIES OF RARE GAS AND MOLECULAR SOLID
FILMS
3.1. Experimental Methods
A number of experimental techniques have been developed to investigate the interaction of
low-energy electrons with atomic and molecular solids. To avoid surface contamination and
to facilitate the use of low-energy electron beams, such experiments must be performed
under ultrahigh-vacuum (UHV) conditions in chambers evacuated by cryogenic, ion, and
turbo-molecular pumps to base pressures below 10
10
Torr. Molecular (and atomic) solid
targets are usually formed by vapor deposition onto a clean substrate held at temperatures of
between 15 and 100 K by a cryostat. The substrate is usually a polycrystalline metal foil, a
metallic monocrystal, or a semiconductor crystal which can be cleaned by resistive heating
and/or ion bombardment. Films of materials that exhibit a high vapor pressure are grown
using a gas-volume expansion dosing procedure [24] that can be calibrated by monitoring the
quantum size eect features observed for ultrathin lms [25]. Films of materials that under
ambient conditions might be described as low vapor pressure solids can be grown using an
oven to generate a low-density molecular ux [26]. Films of larger organic and biomolecular
materials can be prepared ex vacua as self-assembled monolayers on gold substrates [27,28].
Once formed, the sample lms may be probed with a variety of electron beamtechniques, the
most common of which are now briey described.
Low-Energy Electron Transmission Spectroscopy
In a typical low-energy electron transmission (LEET) experiment [24], a trochoidal
monochromator [29] provides an electron current of between 1 and 10 nA, with an
intrinsic resolution between 40 and 60 meV full width at half maximum (fwhm). The beam
is incident normally on the lm surface. A LEET spectrum is obtained by measuring the
current I
t
arriving at the substrate as a function of incident electron energy E
i
. In LEET
spectroscopy, and in the following other electron impact experiments, the absolute energy
scale is calibrated to within F0.15 eV of the vacuum level by measuring the onset of
electron transmission through the lms. A description of the technique is given in Ref. 24.
Charge (Electron) Trapping
The LEET technique [24] can be modied to measure cross sections for charge (electron)
trapping or stabilization by molecules condensed onto dielectric lms [30,31]. Electronic
charge trapped at the surface of a lm, following exposure to electrons of a known E
i
,
produces a retarding potential (DV), which is apparent as a displacement of any
subsequent LEET spectrum to higher incident energies. The observed rate of charging
or charging coecient A
s
can be converted into a charging cross section (r
CT
) as follows:
A
s
E
i
udDVt=dtj
t 0
LIl
o
=epr
2
r
CT
7
where L and e are the spacer layer thickness and dielectric constant, respectively, l
0
is the
surface density of molecular targets, and I and r are the total current and radius of the
incident electron beam, respectively. Absolute trapping cross sections as small as 10
19
cm
2
can be measured with an uncertainty of F50% using this technique. When combined
with the mass spectrometric measurements of the electron-stimulated desorption (ESD) of
anions, r
CT
cross sections can, under certain conditions, allow absolute cross sections for
dissociative electron attachment (DEA) to be obtained.
In the form described above, charge-trapping measurements can only be performed
on nanometer-thick lms. However, analogous measurements on dielectric materials of
macroscopic dimensions (thickness of 0.05 to 0.15 mm and area
f
2 cm
2
) have been
obtained [32] with an instrument that employs a pulsed low-current electron beam (10
14
10
12
C/pulse) to induce charging and a Kelvin probe to measure changes in the samples
surface potential DV. This latter can then be related to changes in the quantity of trapped
charge DQ
t
. Independently obtained electrometer measurements made during each electron
pulse provide an instantaneous measure of the induced charge (e.g., DQ
t
), which, with
knowledge of the incident charge per pulse Q
0
, allows a trapping probability (DQ
t
/Q
0
) to be
determined. The lm is discharged with a UV lamp, mounted outside the vacuum chamber.
High-Resolution Electron Energy-Loss Spectroscopy
The energy losses of electrons scattered near the surface of thin lms and their dependence
on E
i
can be measured with a high-resolution electron energy loss (HREEL) spectrometer
of the type illustrated in Fig. 1. In addition to a cryogenically cooled substrate, such an
instrument includes an electron monochromator and energy analyzer. Those shown in Fig.
1 employ hemispherical electrostatic deectors to achieve optimal resolution (
f
5 to 30
meV fwhm). Typically, the monochromator produces a focused electron beam that strikes
the lm surface at an angle h
0
from the lm normal. Electrons scattered in a narrow pencil
about angle h
r
relative to the surface normal are energy-analyzed with the second hemi-
spherical deector. Dependent on spectrometer design, the angles h
0
, h
r
, or both can be
varied within limits set by available space. Energy-loss spectra are recorded by sweeping
the potential of the monochromator or analyzer relative to the grounded target. The
energy dependence of the magnitude of a given energy-loss event (i.e., the excitation
function) is obtained by sweeping the energy of both deectors with the potential dierence
between them corresponding to the probed energy.
The HREEL technique can be used in several ways: for detailed spectroscopic
studies of vibrational and electronic excitation within the atomic and molecular lms
Figure 1 Schematic representation of a high-resolution electron energy loss (HREEL) spectrometer.
[33,34], for measuring eective elastic and absolute inelastic cross sections [35,36], and for
determining eective cross sections for the production of fragment species [37,38]. This
latter is achieved by measuring the amplitude of a signal associated with a particular
degradation product (for example, a particular electronic or vibrational energy-loss
feature) as a function of the integrated electron current at specic electron energies.
Similar eective cross sections for the production of fragment species may be measured
using x-ray photoelectron [39] and infrared spectroscopies [40].
Electron-Stimulated Desorption Experiments
Electron-induced dissociative processes and certain other reactions are perhaps most
eectively detected when a fragment ion or neutral species is desorbed into vacuum. Gen-
erally, ion desorption is easier to observe than that of neutral species since desorbed
charged particles can be immediately mass-analyzed. Fig. 2 illustrates schematically an
experimental system for ion desorption studies of various types of target including large
organic/biomolecular lms. Note the load-lock section for the introduction sample slides
and/or the degassing of organic molecules within an oven prior to their introduction into
the analysis chamber. In this instrument [26], an electron gun produces an electron beam
of variable energy having a current of between 5 and 300 nA with an energy resolution of
f
250 meV fwhm. The electron beam is incident on a cryogenically cooled solid lm. Ions
desorbed during electron impact enter an ion lens (containing a set of retardation grids)
which precedes a quadrupole mass spectrometer. The so-called ion yield functions are
obtained by recording a particular ion signal as a function of E
i
energy. In other ESD
instruments, the electron gun is replaced with an electrostatic [41,42] or trochoidal [43]
monochromator which produces an electron beam of a few nanoamperes at a resolution
of<80 meV. Pulsed electron sources have also been used [44] in conjunction with a time of
ight mass spectrometer.
Figure 2 Schematic overview of an apparatus suitable for measurements of the electron-stimulated
desorption of anions from vacuum deposited lms. (From Ref. 26.)
In principle, the neutral desorbed products of dissociation can be detected and mass
analyzed, if ionized prior to their introduction into the mass spectrometer. However, such
experiments are dicult due to low eective ionization eciencies for desorbed neutrals.
Nevertheless, a number of systems have been studied in the groups of Wurm et al. [45],
Kimmel et al. [46,47], and Harries et al. [48], for example. In our laboratory, studies of
neutral particle desorption have been concentrated on self-assembled monolayer targets at
room temperature [27,28]. Under certain circumstances, neutrals desorbed in electronically
excited metastable states of sucient energy can be detected by their de-excitation at the
surface of a large-area microchannel plate/detector assembly [49]. Separation of the ESD
signal of metastables from UV luminescence can be eected by time of ight analysis [49];
however, when the photonsignal is small relative tothe metastable yield, such discrimination
is unnecessary and only the total yield of neutral particles (NP) needs to be measured.
3.2. Experimental Results
Elastic and Quasi-Elastic Scattering
Elastic scattering of LEEs by multilayer rare gas and molecular solid lms has been
investigated by low-energy electron transmission (LEET) spectroscopy [24,25,5071],
photoinjection [7282], and elastic reection [35,36,66,8387] experiments. In the latter,
the spectrometer shown in Fig. 1 is adjusted to measure electron elastically scattered from
the lm at particular incident and scattered angles h
0
and h
r
. Then, the amplitude of the
elastic peak is measured as a function of E
i
. Since in these experiments both the incident
and outgoing electron momenta are specied, features due to interferences of the electron
waves are prominent in the spectra. In well-ordered lms, the diraction structure is
dominated by long-range order [66], whereas in amorphous substances, variation in the
structure factor, due to short-range order, can be detected in the energy dependence of the
elastic reectivity [83,84,87].
Both LEET and photoinjection experiments measure the electron current transmitted
through a multilayer lm deposited on a metal substrate. Usually in photoinjection experi-
ments, electrons are injected in the lmfromthe metal substrate with ill-dened energies and
momenta, although some control of electron injection energy is now possible with syn-
chrotron radiation sources [79]. In either case, the outgoing electrons which escape into the
vacuum at a given energy and momentum can be selected with an electron analyzer or
retarding electric eld. This sort of measurement [72] is particularly sensitive to electron
interactions near the substratelm interface and, for self-assembled monolayers of long-
chain organic molecules, to the direction and degree of structural order within the lm [80].
In transmission, it is only the incident beam that has a well-dened energy and
momentum since the current collected at the metal substrate has been scattered into all
angles. Furthermore, when the lm is highly disordered, electrons are scattered in all
possible directions near the surface [53], so that the penetrating momentum is also un-
specied. Electron scattering resulting in multiple energy losses to phonons (i.e., quasi-
elastic scattering) is expected to depend on the electronic conduction band density of states
(CB DOS) and on electronphonon interactions. The calculated CB DOS of solid Ar
(solid line) and that extracted from LEET spectra of multilayer (20100 monolayers) Ar
lms (dashed line) are compared in Fig. 3 [60]. There exists an obvious relationship
between the two sets of data, which indicates that it is essentially the CB DOS that governs
quasi-elastic scattering of the LEEs. In HREEL experiments on rare gas (RG) solids
[83,84], it has been shown that this correspondence arises because of multiple energy losses
to phonons by the scattered electrons. Taking again the example of an Ar multilayer lm,
this relationship is shown in Fig. 4. The curves in the gure were recorded with the
HREEL spectrometer described in Sec. 3.1.3, set to measure the excitation function at an
energy loss DE = 0.25 eV and h
r
= 45j for several incident angles between 15j and 65j.
These curves thus represent the probability that an electron, penetrating a 50-layer lm of
Ar deposited on Pt, loses 0.25 eV via multiple losses to phonons in the solid. Except for the
measurement at h
0
= 45j (i.e., in the specular direction), all features are found at essen-
tially the same energy, independent of the incident angle. The similarity between these
curves reveals an electron-scattering property of the solid that is averaged over various
directions of electron propagation (i.e., various electron states) which may consequently
reect the CB DOS. In Fig. 4(b), the CB DOS of Ar as calculated by Bacalis et al. [88] is
displayed with the bottom of the lowest conduction band xed at the measured value [25]
of 0.25 eV above the vacuum level. Clearly, the experimental curves of Fig. 4(a), especially
those for large incident angles, bare a close resemblance with the calculated CB DOS. The
progressive shift to higher energy of calculated features relative to their experimental coun-
terparts (excluding those peaks at 9 and 12 eV) likely reects a discrepancy between the
face-centered cubic lattice parameter of Ar employed in the calculation (0.526 nm) and
experimental values at 20 K (0.531 nm) [89].
Figure 3 Electron conduction band density of states (CB DOS) for solid Ar; calculated (solid line)
and determined from analysis of LEET data recorded at 20 K at energies below the rst excitonic
threshold (dashed line). The zero of energy is the vacuum level. V
0
is the energy of the bottom of the
conduction band (0.25 eV). (From Ref. 60.)
The similarity between the experimental results and the calculated CB DOS can be
explained by focusing on the electron transport properties in the bulk [83,84]. An electron
propagating in a conduction band of an RG solid suers scattering mainly from defects
and lattice waves. This can be described by introducing the scattering probability per unit
length Q(E
k0
,k
0
,E
k
,k) that a Bloch electron initially in a state jvX of momentum k
0
and
energy E
k0
is scattered into a nal state jv
k
X of momentum k and energy E
k
, while the
crystal changes from a state jiX of energy e
i
to a state j fX of energy e
f
. Then, by referring
to the golden rule and solving the Boltzmann transport equation for a plane-parallel
system in the two-stream approximation [35,36,55,90], one obtains for the electron
mean-free path k(E
i
) (i.e., the reciprocal of Q) the expression
kE
i

X
k
QE
k0
; k
0
; E
k
; k
( )
1
* +
E
i
8
In this expression, the k summation extends over the rst Brillouin zone, whereas h. . .i
Ei
stands for the average over the incident direction k
0
for a constant incident energy. If we
Figure 4 (a) Scattered electron intensity at xed energy loss DE=0.25 eV as a function of incident
electron energy E
i
at several angles of incidence h
0
on a 50-ML (monolayers) Ar lm. (b) CB DOS
for fcc structure of solid Ar as calculated by Bacalis et al. [88]. (From Ref. 83.)
replace the summations with integrations and assume for simplicity that the matrix element
for calculating Q depends only on the momentum transfer (i.e., k k
0
), Eq. (8) yields
kE
i
1
DE
i
h 8p t=XSE
i
f g 1=sE
i
f gi 9
where D(E
i
) is the CB DOS of the solid at the energy E
i
, s(E
i
) corresponds to a relaxation
time (i.e., the time between scattering events) independent of the k
0
direction, S(E
i
) is the
surface of constant energy E
i
within the rst Brillouin zone, and X is the volume of the
crystal. Within the approximations of an electron eective mass and of an electronphonon
interaction described as a deformation-potential perturbation, one has 1/s(E
i
)~k
2
0
and
S(E
0
)~k
2
0
[91]. Consequently, the expression in parentheses in Eq. (9) is independent of E
i
and the energy dependence of k(E
i
)
1
or Q (i.e., the quasi-elastic scattering probability per
unit length) becomes directly proportional to the CBDOS as shown experimentally in Fig. 4.
Inuence of Temporary Electron Trapping on Quasi-Elastic Scattering
and Phonon Creation
The formation of a TNI within an atomic or molecular solid has also been found to aect
quasi-elastic scattering of incident electrons [8587]. A TNI is formed when an electron of
a particular E
i
becomes trapped at a lattice site for a short time (10
15
to 10
13
sec). This
trapping (and detrapping) process transfers energy to the lattice, which appears in HREEL
measurements as an increase in phonon loss processes. The eects of a TNI can thus be
identied by comparing HREELS spectra obtained at the on-resonance electron energy
with those obtained o resonance. The energy and dynamics involved in the temporary
trapping of an electron in a thin solid lm can be demonstrated from electron scattering
experiments on RG solid lms. In RG, an electron resonance occurs at an energy slightly
below the threshold for creating the lowest bulk exciton. In solid Ar, for example, the
lowest transient anion state of Ar
occurs at 11.8 eV and has a lifetime of 2.2 10

14
sec
(approximately 1 order of magnitude less than in the gas phase [85]). This Ar
state is a
core-excited resonance [i.e., a one-hole, two-electron state composed of a 4 s electron
bound to the electronic excited state formed from the atomic orbitals (. . . 3s
2
, 3p
5
, 4s)]. It
has the isolated (i.e., gas phase) conguration (. . . 3s
2
, 3p
5
, 4s
2
)
2
P
3/2
2
P
1/2
. In the
condensed phase, this resonance is 0.25 eV below the n = 1 bulk exciton; it is formed
by the binding of an electron to the n =1,1V (the prime denoting the j =1/2 spin-orbit
partner) excitons in the bulk. The apparent width of the resonance is greater than the spin-
orbit splitting for the neutral exciton states of Ar (
f
0.18 eV [92,93]) so that the state,
assigned as
2
P Ar
, can be considered the unresolved condensed phase equivalent of the

lowest two gas phase Feshbach resonances [94]. Since the anion state involves the coupling
of an electron with an exciton, it is more properly termed as an electronexciton complex.
Fig. 5 shows HREEL spectra obtained with a 12-layer lm of polycrystalline Ar at
h
o
= 15j and h
r
=45j, for incident energies slightly below the n = 1,1V bulk-exciton
thresholds, located at 12.06 and 12.24 eV, respectively [95]. The shaded curve results from
the calculation of the energy-loss distribution [85]. The peak near 0 eV corresponds to
electrons scattered quasi-elastically from the lm. At incident energies E
0
= 11.45 and
12.05 eV, the phonon tail of this latter is characteristic of o-resonance excitation and is
similar to the data recorded at other energies where there are no resonances. However, at
on resonance (i.e., at E
0
= 11.75), the Ar
2
P state is formed and a new phonon peak is
superimposed on the phonon energy-loss tail. Subtracting the o-resonance data from the
HREEL data recorded at E
i
= 11.75 eV provides the contribution to phonon excitation in
the Ar lattice due to the formation of a TNI in solid Ar. The position of the peak in Fig. 5
indicates that the energy released to the surrounding phonon modes by the localization of
an electron at a lattice site during its lifetime is equivalent to that released by about 200
inelastic o-resonance collisions.
The eect of a TNI on the surrounding medium can be described by considering the
interaction between a time-dependent charge located on a lattice site and acoustical
phonons. Using the approach of Mills [96], the result of such an analysis leads to an
expression for the multiphonon loss feature whose intensity and mean energy loss depend
mainly on the electron residence time s
R
and the polarizability of the surrounding atoms
or molecules (i.e., dielectric constant e of the medium). More specically, it can be shown
for a charge e, whose time dependency varies according to e(t) = e exp(jtj/2s
R
) on a lattice
site, that the total probability to excite 1,2, . . . , m, . . . phonons with an energy loss between X
and (X+dX) is given by
dP
tot
dX

X
l
m1
c
m
expc
m!
exp
X mx
2
2mDx
2
" #
2pm
1=2
Dx
10
In this expression, mx and m
1/2
Dx correspond to the mean frequency and width of the m
phonon-loss process, respectively [96]. In the spirit of the Debye model for the longitudinal
acoustic phonon at zero temperature, we have that x=4x
D
/5 and Dx=x
D
2=75
p
with
x
D
the Debye frequency [96]. In Eq. (11), the term c is referred to as the pseudo-Debye
Figure 5 HREEL spectra of a 12-ML Ar lm at three E
i
with h
0
= 15j and analysis angle h
r
= 45j.
At E
i
= 11.75 eV, an Ar
is formed causing an additional peak in the phonon energy-loss tail. The

shaded curve represents the calculated phonon excitation expected from a time-dependent charge at a
lattice site. (From Ref. 85.)
Waller factor because it depends on the transient character of the scattering event, whereas
the usual DebyeWaller factor involves only the overall momentum transfer. It is given
explicitly [96] by
c
8
3
e
4
e 1
2
x
D
s
2
R
tMa
2
0
c
2
l
1 x
D
s
R
2
11
where M is the mass of the atom, a
0
is the nearest neighbor distance, c
1
is the longitudinal
sound velocity, and e is the permittivity appropriate to the frequency range s
R
.
Calculations were performed with Eqs. (10) and (11) with s
R
as the sole adjustable
parameter and experimentally determined values for a
0
, e, x
D
, and c
1
[97]. The result of the
calculation with s
R
= 2.2 10
14
sec is displayed in Fig. 5. Note that the energy of the
maximum is quite sensitive to s
R
; a variation of s
R
by 10% resulted in a 15% change for
the energy of the maximum.
Vibrational Excitation
By scattering within molecular solids and at their surfaces, LEE can excite with consid-
erable cross sections not only phonon modes of the lattice [35,36,83,84,87,90,98,99], but
also individual vibrational levels of the molecular constituents [36,90,98119] of the solid.
These modes can be excited either by nonresonant or by resonant scattering prevailing at
specic energies,* but as will be seen, resonances can enhance this energy-loss process by
orders of magnitude. We provide in the next two subsections specic examples of
vibrational excitation induced by LEE in molecular solid lms. The HREEL spectra of
solid N
2
illustrate well the enhancement of vibrational excitation due to a shape resonance.
The other example with solid O
2
and O
2
-doped Ar further shows the eect of the density
of states on vibrational excitation.
High-Resolution Electron Energy-Loss Spectra of N
2
. Vibrational excitation of
ground-state N
2
, induced by LEE impact on thin multilayer N
2
lms, is illustrated in
Fig. 6. These electron energy-loss spectra were recorded for electrons of energies E
i
= 2.9,
10.8, and 19.8 eV, h
o
= 14j and h
r
= 45j. The vertical gain in each curve or portion of a
curve is referenced to the elastic peak. Each energy-loss peak can be ascribed to vibrational
excitation of ground-state N
2
[100]. It can be seen in the gure that at certain impact
energies (E
i
= 2.9 and 19.8 eV), the intensities of vibrational energy losses are greatly
increased (i.e., up to 2 orders of magnitude for overtones). In N
2
lms, the production of
overtones at E
i
= 2.9 and 20 eV is attributable to
2
C
g
and
2
A
u
shape resonances [100].
There is, however, no electron resonance at E
i
= 10.8 eV in N
2
so that the strongest part
of the interaction leading to vibrational excitation arises mainly from induced polarization
(i.e., from direct scattering). This interaction is mainly eective to produce excitation of
one vibrational quantum which amounts to an energy loss of less than 0.4 eV.
Excitation Functions of O
2
and O
2
-Doped Ar Films. Resonances can be best
identied by the structures they produce in excitation functions of a particular energy-
loss process (i.e., the incident-electron energy dependence of the loss). Fig. 7 is reproduced
from a recent study [118] of the electron-induced vibrational and electronic excitation of
multilayer lms of O
2
condensed on the Pt(111) surface and shows the incident electron
energy dependence of major losses at the indicated lm thickness and scattering angles.
Also shown in this gure is the scattered electron intensity of the inelastic background
* For a theoretical description of the eects of a surface on resonant scattering, see Ref. 120.
located just before the v=1 peak onset at DE=0.16 eV along with that contributing to
each energy loss (dashed lines).
With the exception of that of the a
1
D
g
(v=0) loss, the vibrational excitation
functions of O
2
in the solid phase dier signicantly from their gas-phase equivalents.
For example, the well-known sharp peaks of the
2
C
g
resonance, which dominate the
vibrational cross sections up to 3 eV in the gas phase [121], are absent in the solid phase.
This absence is understood as deriving from a lowering in energy of the
2
C
g
resonance by
charge-image/charge polarization [101] of the O
2
lm. At higher energies in the gas phase,
excitation functions for the X
3
A
g
, v=1, 2, and 3 vibrational losses display a single
structure due to the
2
C
u
resonance near 6.5 eV. In contrast, in the condensed phase, the
same vibrational losses are characterized by three broad overlapping bands, attributed to
the excitation of the
2
C
u
,
2
A
g
I,
2
A
u
(I), and
2
A
g;u
(II) anion states at 6.5, 8.5, 10.5, and 13.5
eV, respectively. These contributions from A
+
transient anion states, which are forbidden
by the mirror plane symmetry selection rule in the gas phase (i.e., A
p/
!
A
+
), arise here
due to the loss of the cylindrical symmetry of O
2
in the condensed phase [122].
The vibrational excitation is further altered when O
2
molecules are embedded within
an Ar matrix [118,119]. Fig. 8 presents the results of experiments for 1% O
2
in 20 ML of Ar
and shows excitation functions for the v=1 and 2 vibrational losses of O
2
[Fig. 8(b) and (c),
Figure 6 HREEL spectra of a multilayer disordered N
2
lm recorded at the indicated E
i
. (From
Ref. 100.)
respectively] obtained after subtraction of a background of Ar phonon losses. Compared to
the gas-phase result [121] [shown in Fig. 8(a) for v = 1], and those for solid O
2
in Fig. 7, the
excitation functions for O
2
in Ar are much more structured, containing many narrow
features. There is also a signicant vibrational enhancement within the 2.55 eV incident
energy range that is absent in the pure multilayer O
2
results (Fig. 7). Furthermore, except for
the relative intensity changes, each maximum is located at the same energy independently of
the angle of incidence and azimuthal orientation of the crystal. Such a behavior strongly
suggests that the maxima arise primarily from an electron scattering property that is
averaged over various directions of electron propagation within the crystal and thus
depends on the CB DOS. In Fig. 8(d), we again reproduce the CB DOS of solid Ar [88]
Figure 7 Incident electron energy dependence of the X
3
A
g
, v = 0, 1, 2, 3 vibrational and the a
1
D
g
(v = 0) electronic loss scattered intensities from a 10-layer lm of O
2
condensed on Pt(111). h
0
was
set at 10j with h
r
at 45j and the azimuth /
0
at 10j. Also shown is the energy dependence of the
inelastic background intensity located just before the v = 1 loss peak onset at DE = 0.16 eV along
with that contributing to each energy-loss prole (dashed lines). (From Ref. 118.)
and it is easily seen that all maxima in Fig. 8(b) and (c) correlate respectively with minima in
the CB DOS as opposed to the scattered intensity arising from multiple scattering on
phonon (Fig. 4) [83,84], which was shown to follow the CB DOS.
This striking result can be qualitatively understood as related to CB DOS-inuenced
changes in the O
2
anion lifetime [118]. For a diatomic molecule with R as the internuclear

coordinate, a transient anion state is described in the xed nuclei limit [123,124] by an
energy and R-dependent complex potential: V
opt
(R,E
i
) = V
d
(R) +D(E
i
)1/2iC(E
i
), where
V
d
(R) u e
d
(R) + V
G
(R) is the potential energy curve of the discrete state, V
G
(R) is the
potential energy curve of the ground state, and E
i
is the kinetic energy of the scattered
electron. The electronic decay width function C(E
i
) is given explicitly by
CE
i
t=sE
i
2p
X
k
V
d;k
2
dE
i
E
k
i2p V
d;E
2
DE
i
; 12
Figure 8 (a) Dierential cross section for the excitation of X
3
A
g
, v = 1 vibrational level of gaseous
O
2
. (b) and (c) are the incident electron energy dependence of the net v =1, 2 energy-loss intensities for
a 20-ML lm of 1% O
2
in Ar. (d) is the CB DOS of solid Ar. (From Ref. 119.)
where V
d,k
is the coupling matrix element responsible for the decay and E
k
is the energy of
the free electron continuum. Under suciently small variations of the matrix element with
the wave vector k, the density of free electron states D(E) appears explicitly with the
summation over k [125].
For the short capture time limit, it can be shown [118] that the energy imparted to
the nuclei DT
N
can be approximated by
DT
N
i2M
red
1
F
2
r
R
i
s
2
E
r
R
i
; 13
where M
red
is the reduced mass of the molecule, s is the anion lifetime, E
r
is the energy of
the resonance, R
i
is the internuclear separation at which attachment occurs, and F
r
is the
internuclear force. It is apparent that the energy DT
N
is a combination of two factors: the
strength of the resonant vibrational coupling F
r
(R) (which depends on the shape of
internuclear potential of the TNI) and the resonance lifetime s[E
r
(R)]. In the absence of
potential energy curve crossings within the FranckCondon region, the factor F
r
(R) in Eq.
(13) varies slowly as a function of the R. Moreover, as the transient anion potential energy
curve is in a rst approximation only slightly shifted down by the polarization of the sur-
rounding medium, F
r
(R) is virtually the same in both gas and condensed phase.
On the other hand, the lifetime of the resonance s[E
r
(R)], whose inverse is explicitly
given by s
1
[E
r
(R)]i(2p/t)jV
d,Er
j
2
D[E
r
(R)] [cf., Eq. (12)], is directly linked to the CB DOS
of the host medium, i.e., D[E
r
(R)]. The remaining factor, which contains the matrix
element responsible for the decay V
d,Er
, is akin to a tunneling eect and yields essentially a
monotonic behavior in energy. Owing to its relatively short-range character, it is also
expected not to change signicantly between gas and condensed phases. Consequently, the
amount of energy transferred to the nuclei [cf., Eq. (13)] along with the corresponding
overtone scattering probabilities (i.e., cross sections) varies mostly, via the modication of
the resonance lifetime, as the opposite of the CB DOS of the host medium.
Electronic Excitation
Electron Spectroscopy. Electronic excitation induced by LEE in multilayer in
atomic and molecular solids has been studied with LEET [24,51,52,57,62,126131] and
HREELS [104,131147]. The slow-electron excitation of electronic states of atoms and
nondissociative electronic states of molecules in dielectrics can result in localized energy
deposits (e.g., Refs. 136 and 137) or into the formation of excitons [133] that propagate
through the solid with well-dened wave vector. From HREELS measurements, one notes
that electronic excitation in a molecular solids is similar and of similar magnitude to that
observed for the isolated molecule, except for the cases of Rydberg and symmetry-
forbidden transitions. It appears that a general characteristic of Rydberg states in con-
densed phases is poorly resolved since they broaden considerably into wide bands [148]
due to autoionization by fast exchange of Rydberg electrons. In contrast, the strong
exchange interaction in the low-energy regime causes singlettriplet transitions to be more
prominent in low-energy HREEL spectra than in measurements obtained with higher-
energy electrons or photon excitation. Consequently, the low-energy HREELS has
employed intensively to study the lowest triplet states of organic molecules [135146].
Electron-Stimulated Desorption of Metastable Species. Electronic excitation of
atomic and molecular solids is also demonstrated in the ESD yield of metastable atoms
and molecules (i.e., lifetimes >10
6
sec) and of UV photons from RG solids Ne and Ar
[49,149151], RG alloys [152], and from molecular solids of N
2
[153], N
2
O [154], CO
[153,155], and CO
2
[156,157], as well as N
2
- and CO-covered Xe and Kr [158160].
Desorption can proceed via several mechanisms. For solids with a negative electron
anity such as Ar [49,149151] and N
2
[153], the extended electron cloud around a
metastable center will interact repulsively with the surrounding medium and metastables
formed at the lmvacuum interface will be expelled into vacuum (the so-called cavity
expulsion mechanism [161]). Also permitted in solids with positive electron anities (e.g.,
CO) is the transfer of energy intramolecular vibration to the molecule-surface bond with
the resulting desorption of a molecule in lower vibrational level [153,155,158160].
Desorption of metastables via the excitation of dissociative molecular (or excimer)
electronic states is also possible [49,149151,154,156,157]. A concise review of the topic
can be found in Ref. 162.
Recent measurements have presented an interesting example of how metastable
desorption can provide information on TNI electronic excitation in rare gas solids. Low-
energy electron impact on solid Ar is known to induce the desorption of metastable Ar
atoms (Ar*) [49,149] via the repulsive interaction of a surface-trapped exciton with the
surrounding ground-state Ar atoms [161]. Fig. 9(b)(e) shows NP yield functions from
thin Ar lms of varying preparation [163,164]. The signal at energies above 12 eV is
correlated to the production of neutral excitons within the lm and their decay by ejection
and/or photon luminescence [151]. The maximum NP yield at
f
15 eV coincides with the
energy for optimum production of excited states in the gas [165] and condensed phases
[151]. What is of note, however, in the data of Fig. 9 is that the
2
P Ar
, shown in the
HREEL data of Fig. 9(a), also contributes to the NP signal seen from the
f
11.5 eV peak
in each of the NP yield functions of Fig. 9(b), (d), and (e). This is surprising since the
2
P
Ar
resonance lies below the energy of the rst bulk and surface Ar excitons found at 12.03
and 11.71 eV [133], so that its observation in NP (and metastable) yield functions implies
that the resonance has decayed into the higher-lying exciton energy levels [163]! In detailed
studies of the
2
P Ar
, as a function of Ar lm thickness [163] and in Ar/n-hexane double-

layer systems [164], it has been shown that Ar* desorption is initiated by electron emission
from Ar
to the Pt(111) substrate at an energy of about 0.3 eV below the vacuum level.
After electron emission at the Ar/Pt(111) interface, Ar* in the form of an exciton moves to
the lmvacuum interface, where it can be ejected. Autoionization to the metal is inhibited
when a spacer layer is introduced between the Ar layer and the substrate as evidenced in
Fig. 9(c), where the resonance signal disappears for Ar condensed on a spacer of 3 ML of
crystalline n-hexane.
The remaining results in Fig. 9 demonstrate that when a small amount of molecular
oxygen is mixed in the Ar layer condensed on n-hexane [Fig. 9(e)] or deposited onto an
isolated Ar layer [Fig. 9(d)], the
2
P Ar
resonance reappears in the Ar* desorption yield

function. Since the n-hexane spacer inhibits Ar
decay by electron transfer to Pt(111), the

presence of
2
P Ar
resonance in Fig. 9(c) and (d) was therefore interpreted [164] as due to
electron transfer to O
2
leading to the formation of O
2
in its ground-state
2
C
g
. With the
electron anity of O
2
being of the order of the binding energy of the rst electronically
excited state of Ar, the decay of Ar
2
P into lowest bulk excitons is possible by electron
transfer to O
2
.
Stable Anion Formation
The production of stable anions by low-energy electron impact has been studied by ESD
[22,41,43,44,122,147,154,156,157,166219] and charge-trapping [154,156,217,220236]
experiments. Below 20 eV, the desorption of stable anions from condensed systems is
attributed to DEA, which produces oscillatory structures in the anion yield functions, and
to dipolar dissociation (DD), which produces both anionic and cationic fragments.
Typically, DD produces a featureless signal which increases linearly with electron energy
from a threshold lying between 10 and 20 eV. Anion desorption data are often dominated
by the DEA process. The rst observations of DEA in a solid were made from the ESD of
O
from multilayer O
2
lms [166]. Subsequently, the O
2
molecule has served as a model
target to study factors aecting the physics of DEA in condensed phase systems
[41,122,172175,184,185,188191,206,209,211]. The yield of O
from electron impact on

gas phase and multilayer-condensed O
2
is shown in Fig. 10(a) and (b), respectively. In the
Figure 9 (a) High-resolution electron energy loss (HREEL) excitation function of 4 ML of Ar
obtained at an energy loss DE = 0.75 eV [85]. Neutral particle yield function produced by electron
impact on: (b) 2 ML of Ar; (c) 2 ML of Ar condensed on a 3 ML crystalline n-hexane (nH) spacer
layer; (d) same as in (c) but with 0.25 ML of O
2
adsorbed on the lm surface; and (e) same as (c) but
with 2 ML of Ar containing 10% volume of O
2
adsorbed on the nH lm. In all cases, the substrate is
Pt(111). (From Refs. 163 and 164.)
gas phase, the O
signal is dominated by DEA via the

2
C
u
state of O
2
at
f
6.7 eV [237].
In contrast, the anion yield function from multilayer O
2
shows in addition to DD above
f
15 eV a much broader resonance feature between 5 and 10 eV and another structure at
13 eV. The broadening of the lower energy structure and the appearance of the 13-eV
structure are attributed to DEA via A
+
states following a relaxation of the A
===
A
+
selection rule [122].
Also shown in Fig. 10(c)(g) are the anion yield functions for submonolayer
quantities of O
2
deposited onto various multilayer atomic and molecular solids. The data
represent part of a study [41] on the environmental factors involved in the DEA process.
As can be seen, the yield of desorbed ions can vary greatly with substrate composition.
Such variations can be attributed to the so-called extrinsic factors that modify the ESD
process at times before attachment and after dissociation, for example, electron energy-
loss processes in the substrate and postdissociation interactions (PDI) of ions with the
surrounding medium [41]. These processes can be contrasted with intrinsic factors, which
Figure 10 O
yield functions for electron impact on (a) gaseous O

2
, (b) 4 ML of O
2
, and (cg) 0.15
MLof O
2
condensed on 4 MLof the indicated substrate. The dashed lines and bars indicate the known
positions of the O
2
resonances. The gain factor over each curve is relative to curve (c), and the shifted
baselines correspond to the zero anion intensity levels. Figure based on the data of Ref. 41.
modify the properties of the resonance (e.g., lifetime, energy, and decay channels). In
general, the O
yields per O
2
molecule are higher for O
2
deposited on RG solids Kr and
Xe [Fig. 10(c) and (d)see Ref. 211 for detailed comparison of O
desorption from RG
solids] than on a molecular solid where extrinsic eects such as electron energy-loss
processes and PDI are more likely. The weakest O
signal was observed from O

2
on H
2
O
[Fig. 10(g)] which, like the other substrate lms, was condensed at temperature of 20 K.
The gure shows that while the DD signal is reduced by approximately a factor of 100
relative to O
2
on Kr, the O
ESD signal over the energy range associated with DEA is

almost entirely absent. This dramatic eect (termed quenching) was initially attributed to
some interaction of the transient O
2
states with the dipole moment of the adjacent water

molecules [175]. However, later work [206,238,239] has shown that amorphous water lms
formed at 20 K can be highly porous. When O
2
is deposited onto porous ice at 20 K (close
to the sublimation temperature of oxygen), it diuses rapidly over the lms extended
surface, so that the eective density of O
2
at the lmvacuum interface is lowered
considerably from that obtained when the same quantity is deposited onto a nonporous
lm. Oxygen ions formed inside the lm have a much lower probability of desorption than
those generated at the lmvacuum since they are more likely to scatter and lose kinetic
energy [206]. Absolute cross sections for anion desorption and hence lower limits for DEA
cross sections have been reported for O
from O
3
[203] and CF
3
I [200]. By combining ESD
data with the results of charge-trapping experiments, DEA cross sections have also been
from H
2
O, [222,223], CF
4
[224,225], CF
3
Cl [230,231,233], HCl [236], CF
2
Cl
2
[235], CH
3
Br
[227], and the chloromethanes [226229,231].
The E
i
dependence of the surface charging cross section r
CT
for 0.1 ML of CH
3
Cl
condensed onto a 15-ML Kr lm [226,227] is shown in Fig. 11(a). The two curves Fig.
11(b) and (c) show the H
and Cl
ESD yield functions for similar quantity of CH

3
Cl
deposited onto a 7-ML Kr lm [182]. No ESD signal was detected below 5 eV. Curve Fig.
11(d) is the total anion yield from the gas phase as measured by Pearl and Burrow [240]
and was obtained by subtracting a background signal at 0 eV arising from CCl
4
. The
0.8-eV peak in this curve represents a cross section of (2.0F0.4) 10
21
cm
2
for anion
production, a value much smaller than that of (13F2) 10
18
cm
2
for the 0.5-eV peak in
Fig. 11(a). Moreover, the origin of this gas phase structure has been questioned, as its
variation of magnitude with increasing temperature is consistent with the DEA of HCl
[240].
The variation with Kr lm thickness of the amplitude (full squares) and energy at
maximum (open squares) of the lowest energy charge-trapping cross section feature is
shown in Fig. 12. It is apparent that both these quantities are strongly dependent on Kr
lm thickness. The thickness dependence of the features energy is reminiscent of that
observed by Michaud and Sanche [103] in the energy of the
2
C
g
resonance of N
2
on Ar,
which was successfully described in terms of the polarizability of the Ar lm and the image
charge induced in the metal substrate. The lower dashed curve is a t to the data of the
same type of function used by Michaud and Sanche to describe the thickness-dependent
changes in polarization energy V
p
[103].
The structure near 0.5 eV in Fig. 11(a) has been interpreted [226,227] as due to the
formation of Cl
anions via DEA to the

2
A
1
state of CH
3
Cl
and the subsequent

dissociation of Cl
and CH
3
along the strongly antibonding CCl
r* orbital. Since no
ESD signal is observed in Fig. 11(b) and (c) below 5 eV, the charge-trapping cross section
represents an absolute DEA cross section at these low energies. The value reported for
CH
3
Cl on a 5-ML-thick Kr lm (Fig. 12) thus represents an enhancement over gas-phase
experimental [240] and theoretical values [241] of between 4 and 6 orders of magnitude,
respectively. This remarkable enhancement has been attributed to image-charge-induced
polarization energy V
p
, which lowers the potential energy curve of the intermediate
transient anion increasing the anion lifetime [242] and decreasing the distance the anion
must stretch before dissociation is inevitable [226,227].
A quantitative understanding of the eect of V
p
on electron attachment to CH
3
Cl
adsorbed on Kr [226,226] and within its bulk [229] has been attempted with a modied
version of the R-matrix scattering model [241] which has been previously successful in
describing LEECH
3
Cl scattering in the gas phase [243]. Essentially, the model was
modied to include the eects of V
p
at short electronmolecule distances. The solid line in
Fig. 12 represents the results of the R-matrix calculation. However, to obtain this result, it
was also necessary to model in a semi-empirical fashion the electrons interaction with the
metal substrate. The discontinuity represented by the lms surface complicates consid-
erably this type of calculation, which is more straightforward for CH
3
Cl embedded within
bulk Kr. In this case [229], good agreement between theory and experiment is possible by
adjusting V
p
alone. However, it must be noted that the values of V
p
required to t the data
Figure 11 Charging cross section and anion yields induced by 010 eV electron impact on CH
3
Cl.
(a) Absolute surface charging cross section for 0.1 ML methyl chloride condensed on a 15-ML Kr
lm. (b) H
and Cl
desorption yields. (c) Total anion yield from gaseous methyl chloride. Figure
taken from Ref. 227.
for CH
3
Cl condensed on and within Kr are approximately 50% larger than those
measured elsewhere in other experiments [103]. With these latter values, the calculated
cross sections are about 1 order of magnitude too small. This disparity does not exist when
comparing similar charging data for CF
3
Cl [230] with an R-matrix calculation [231].
Comparison of the CH
3
Cl and CF
3
Cl data and calculations [231] suggest that the CH
3
Cl
PE curve may be modied in the Kr environment due to a change of symmetry and/or

screening of the CH
3
and Cl
interaction by the Kr medium at intermediate internuclear

separations. Alternatively, Aatooni and Burrow have suggested that the eective polar-
ization energy seen by CH
3
Cl on Kr could indeed be larger than that measured for N
2
on
Kr [103] due to the larger static dipole moment of this molecule.
Two further mechanisms are known to trap electronic charge in thin lms:
intermolecular and resonance stabilization. In resonance stabilization, electron attachment
to a molecular center produces an anion in a vibrationally excited state that is then de-
excited by energy exchange with neighboring molecules. When the initial anion ground
state lies below the band edge or lowest conduction level of the dielectric, then the
additional electron may become permanently trapped at the molecular site. In this case, a
permanent anion is formed (e.g., the case of O
2
[220]). Intermolecular stabilization refers
Figure 12 (a) Variation of maximum charge-trapping cross section (r
CT
) with Kr lm thickness
for low-energy electrons incident on 0.1 ML of CH
3
Cl deposited on the surface of Kr lms. The solid
line drawn from the data represents the results of an R-matrix calculation to describe electron
CH
3
Cl/Kr scattering. (b) Variation in energy E
max
of the maximum in r
CT
with Kr lm thickness.
Dashed line is a parametric t to E
max
. (From Ref. 226.)
to the trapping of a LEE by an aggregate of molecules, typically unable to do so in the
monomeric form. In this sense, the process is similar to solvation,* which usually requires
the organization of polar molecules to form a suitable trap. Intermolecular stabilization
has been observed for water clusters condensed on Kr and Xe surfaces at cryogenic
temperatures [222] and in pure water lms [223]. Both intermolecular and resonance
stabilization occur at incident electron energies below 1 eV. Since DEA can, in some
systems, occur at similar energies, it is not always easy to identify which process is
responsible for charge accumulation. Fortunately, further information can sometimes be
obtained from measurements of the ESD yield of anions from similar lms and from
comparison with gas phase results.
Electron Transfer from the Environment
In general, the properties of molecular TNI of condensed molecules are greatly aected by
their local environment. It is unsurprising then to nd that DEA can arise from electron
transfer from an electron state of the substrate to a dopant molecule. Such a transfer has
been observed between the electronexciton complex of RGS and adsorbed molecules
[179,180], between water lms and adsorbed CF
2
Cl
2
[235] and HCl [236], and between
image states and CH
3
Cl [232]. Fig. 13 presents recent charge-trapping data obtained on
10-ML-thick lms of n-hexane [232]. Fig 13(a) represents the energy variation of the
trapping coecient for pure n-hexane in the glassy amorphous state nH
g
that forms by
vacuum deposition at 25 K [245].
y
The curve shows that below E
i
= 7 eV, the threshold for
charging via DEA to n-hexane [167], charging coecients are very small. Annealing such
lms at 60 K produces crystalline n-hexane nH
c
, which is also resistant to charging
below 7 eV [Fig 13(b)]. It is this property of both n-hexane lm types (i.e., resistance to
charging) which renders them suitable substrates to study electron attachment to surface
dopant molecules at incident electron energies below 7 eV. Fig 13(c) presents A
s
(E
i
) for 0.1
ML CH
3
Cl on the surface of a 5-ML nH
g
lm. The sharp (50 meV fwhm) and intense peak
near zero energy is shown on an extended energy scale in the inset [Fig 13(d)]. The
maximum in A
s
corresponds to a charge-trapping cross section of 2 10
13
cm
2
which is
10
4
times larger than that for DEA to CH
3
Cl on the Kr lm surface [226] shown in Fig
13(e). Charging data for 0.1 ML CH
3
Cl on the nH
c
lm surface are shown in Fig 13(f) and
do not show the same intense charging at 0 eV seen on the glassy n-hexane substrate. The
DEA peak observed near 0.5 eV for CH
3
Cl on Kr [in Fig 13(e)] is hidden by the back-
ground signal in Fig 13(f).
Likewise, large charge-trapping cross sections, peaked sharply at 0 eV, were
measured for submonolayer quantities of O
2
and H
2
O deposited onto the nH
g
substrate.
Both of these molecules are known to trap near-zero electron volt electrons (as O
2
[220]
and by intermolecular stabilization within water assemblages [222]), but again, the cross
sections on nH
g
were several orders of magnitude larger than when measured on Kr or on
nH
c
lms. Signicantly, charging coecients (and the cross sections for electron trapping)
at higher energies on the nH
g
surface were not enhanced, and no 0-eV peak was observed
in charge-trapping measurements for CF
4
on nH
g
(CF
4
on Kr does not trap near 0 eV
electrons [224]). In light of these results, viz., a huge enhancement in A
s
(E
i
) at 0 eV,
independent of the mechanism of electron stabilization (but only for molecules that trap
* See, e.g., Ref. 244.
y
More recent studies (Ref. 239) have shown n-hexane lms formed at <60 K to be highly porous,
although this fact is not of great relevance to the present discussion.
electrons near 0 eV), it was argued that trapping proceeds via the initial capture of the
electron into an image state of the substrate with subsequent resonant transfer of the
surface electron to the molecular target [e.g., O
2
, CH
3
Cl, or (H
2
O)
n
]. Since in this case a
large portion of the surface would be available for electron capture, the observed large
trapping cross sections would likely result, provided that the lifetime of the electron in the
image state near the surface was suciently long. Fig. 14(a) explains this process in more
detail and shows schematically the band structure near the surface of the glassy n-hexane
as deduced from the information contained in the LEET spectra of nH
g
[55]. The nH
g
lm
has a band gap at the vacuum level with the lowest conduction band edge lying at V
0
= 0.8
eV [55]. This latter, combined with the attractive interaction of an incident electron with its
image charge, produces at the lmvacuum interface a potential well of a sucient depth
to support quasi-bound electron state(s). A realistic calculation for the nH
g
system [232]
predicts image states at 0.1 and 0.42 eV below the vacuum level with lifetimes greater than
3 nsec, assuming the decay of the image state via electron transfer through gap states.
Figure 13 Charging coecient A
s
(E
i
) as a function of incident electron energy E
i
for (a) a 10-ML
lm of glassy n-hexane nH
g
; (b) a 13-ML lm of crystalline n-hexane nH
c
; (c) 0.1 ML CH
3
Cl on a 5-
ML nH
g
surface; (d) the peak near zero energy in (c) shown on an extended scale; (e) 0.1 ML CH
3
Cl
on a 10-ML Kr surface; (f) 0.1 ML CH
3
Cl on 13 ML nH
c
surface. (From Ref. 232.)
Normally incident near-zero electron volt electrons scattered into nonspecular directions
will be captured into these states. While the image states are themselves too short-lived to
contribute to charge coecient measurements, the calculated lifetime is much longer than
phonon vibrational periods, so that the probability that the excess electron transfer to any
electron acceptor, be it O
2
, CH
3
Cl, or (H
2
O)
n
clusters, would be large. In contrast, on Kr
and nH
c
lms, the conduction band edge is lower [Fig. 14 (b)] [232] and the potential well
at the lmvacuum interface is no longer capable of supporting an image state of sucient
lifetime to transfer to the adsorbate.
Figure 14 Schematic diagram of simplied one-dimensional band structure for an nH
g
(top) and
Kr (bottom) spacer layer lm. (From Ref. 232.)
Electron-Induced Reactions
Impact of LEE on atomic and molecular solids has been observed to induce chemical
changes other than dissociation. In the next two sections, we will review examples of elec-
tron-induced reactions that proceed via formation of a TNI.
Anion Desorption Measurements. Reactive scattering by DEA fragment ions in con-
densed media was rst noted in the form of OH
electron-stimulated desorption (ESD)

yields from O
2
embedded in multilayer alkane lms [246] and subsequently for aniline
physisorbed on top of O
2
solids [215]. The O
anion produced following DEA to N

2
O has
also been observed to react with other N
2
Omolecules within an Ar/N
2
Omatrix to generate a
desorbed yield of NO
and NO
2
, among other products. Part of the H

2
ESD yield observed
from multilayer lms of H
2
O, at incident electron energies below 10 eV, has also been attri-
buted to proton abstraction by H
fragments produced by DEA, viz., H
+H
2
O!{H
3
O}*
!H
2
+OH
[46], and has thus been associated with part of the unscavengeable H
2
yield
formed in water radiolysis [247]. Another (post-DEA) ionmolecule reaction, directly
observed in the condensed phase for ion kinetic energies well below5 eV, is isotope exchange
measured in
18
O
2
/C
16
Omixed solids [248], i.e.,
18
O
+C
16
O!{C
18
O
16
O}*
18
!O
+C
18
O.
Formation of D
2
O in synchrotron-irradiated lms of N
2
O has also been attributed to
associative electron attachment reactions of DEA O
fragments with matrix D

2
molecules,
i.e., O
+D
2
!D
2
O*
!D
2
O+e
[249]. Measurements of electron-stimulated O

3
produc-
tion in condensed O
2
lms were attributed to postdissociation reactions of neutral O(
3
P, or
1
D) with adjacent molecules [250]. The threshold energy for this process being near 3.5 eV
allowed DEA to be identied as the source of O(
3
P) at low incident electron energies.
Similarly, Hedhili et al. [251], in their measurements of F
and Cl
desorption from
condensed CF
2
Cl
2
, have observed the appearance of new features in the Cl
yield function
at long bombardment times. These changes were attributed to the synthesis of Cl
2
in the
condensed phase by an as yet unidentied reaction pathway having DEA to CF
2
Cl
2
as its
initial step. Subsequent measurements of Cl
desorption from LEE impact on lms of 1,2-

C
2
F
4
Cl
2
also show the production of Cl
2
and the cross section for formation of which
exhibits maxima at near 0 and 10 eV. While Cl
2
production at the higher energy may involve
either excited anionic or electronic molecular states, at energies below 2 eV, it can only be
initiated by DEA. In other experiments, Tegeder and Illenberger [252] have shown, by
comparison of anion ESDdata and infraredabsorptionreection spectroscopy, that DEA
is the initial step in the production of N
2
F
4
molecules within NF
3
lms under bombardment
with 0 to 5 eV electrons.
In early studies of anion desorption fromsolid O
2
/hydrocarbon mixtures [246], several
observations were made concerning the desorbed signal of OH
. (1) The OH
yield
functions resembled more closely the yield functions for O
with kinetic energies 1.5 eV

frompure O
2
lms than the H
signal associated with DEAto the hydrocarbon molecule. (2)

The OH
signal froman O
2
lmincreased linearly with alkane surface coverage below1 ML.
(3) The threshold in energy for OH
desorption coincided with that for O
desorption,
which is at least 2 eVbelow the H
desorption onset. For these reasons, and the fact that O

2
is the only charged product observed inthe gas-phase collisions of H
withO
2
[253], the OH
desorption signal was attributed to hydrogen abstraction reactions of the type

O
C
n
H
m
! C
n
H
m
O*
! OH
C
n
H
m1
The existence of such C
n
H
m
O*
intermediate anion collision complex had previously been

suggested by Comer and Schulz [254], who measured the energies of electrons emitted during
gas-phase collisions of O
with C
2
H
4
. Further evidence for a complex anion formation and
reactive scattering in the gas phase can be seen in the studies of Parkes [255] and Lindinger
et al. [256].
More recent measurements [257] reproduced in Fig. 15(a) show the H
yield vs. E
i
.
An enhanced H
signal at low E
i
is observed from the O
2
/C
4
H
10
mixed lms. Two trends
can be observed in Fig. 15(a) with increasing O
2
concentration. Firstly, there is a decrease
in the yield of H
at 10 eV, the peak energy of H
production via direct DEA to the alkane

molecule. Secondly, there is the appearance and the development of a second H
ESD
structure at lower energies, such that at an O
2
concentration of 20%, a substantial fraction
of the H
yield occurs at incident electron energies signicantly below those required for
DEA to C
4
H
10
. In Fig. 15(b), the H
yield function from an n-butane lm containing 10%

O
2
by volume curve (1) is resolved into two separate components. One of these, with a
maximum at 10 eV (dotted curve), is assumed identical in form to that of H
desorption
from pure C
4
H
10
. The other (bold curve 2) is obtained from curve (1) when the H
signal
from a pure lm normalized to curve (1) at 10 eV (dotted line) is removed. This procedure
yields a second quasi-Gaussian-shaped structure centered at 7.8 eV, close to the energy of
maximum production of O
via DEA and with a threshold at 5.5 eV, identical to that

observed for OH
production. From these observations, the increase in H
production at
incident electron energies below the threshold for DEA to C
4
H
10
was attributed to reactive
scattering of O
and atom-exchange reactions of the type

O
C
4
H
10
! C
4
H
10
O*
! H
C
4
H
9
O
Figure 15 (a) The H
yield function from 4-ML-thick lms of an O

2
/C
4
H
10
mixture of increasing
percentage volume concentration of O
2
. (b) The H
signal from a 4-ML-thick mixture of 10% O

2
in
C
4
H
10
can be resolved into two components: one centered at 10 eV, associated with H
production
via DEA to the alkane (dotted line), and another at 7.8 eV, associated with reactive scattering of O
ions (bold line). Also shown is the yield of OH
ions from the same lm. (From Ref. 257.)

involving the same or similar transient anions as those responsible for OH
production, as
evidenced from the similarity of the OH
and H
yield functions in Fig. 15(b). Evidence

for additional channels in the decay of such C
n
H
m
O*
anions was apparent in the anion

yield functions of CH
and CH
2
from thin lms of C

2
H
4
/O
2
mixtures [257] as a sub-DEA
threshold component to the anion signals.
Electron-Induced ReactionsHREELS Measurements. Novel LEE-induced chem-
istry has also been observed in HREEL measurements of molecular solids and molecules
physisorbed on the surface of RGS. For example, Lepage et al., building on the initial
observations of Jay-Gerin et al. [141], have employed HREELS to measure in situ, neutral
dissociation products arising from the impact of low-energy electrons on thin multilayer
lms of methanol [37] and acetone [38]. The technique is similar to that developed earlier by
Martel et al. [258] for chemisorbed systems, in that the same electron beam is used for both
the production and the detection of the neutral fragments. However, in the work of Lepage
Figure 16 Electron energy-loss spectra with 14-eVelectrons incident on: (a) a 5-MLlmof methanol
condensed on an Ar spacer after exposition to small (lower curve) and large (higher curve) electron
doses and (b) a 10-ML lm of CO condensed on a platinum substrate. The a
3
C excited state of CO is
characterized by a vibrational progression having a spacing of about 0.21 eV. (From Ref. 37.)
et al., neutrals are detected via their electronic excitation rather than by the spectroscopy of
their vibrational levels. Fig. 16(a) shows HREEL spectra of multilayer methanol (CH
3
OH)
for energy losses in the range 5.5 to 7.5 eV. The incident electron energy was 14 eV. The lower
curve in Fig. 16 was taken after 5 min of electron bombardment of the CH
3
OH lm. A weak
structure is visible in the spectrum at energies below 6.7 eV. The upper curve was recorded
after 20 min of exposure to the 14-eV electron beam and shows the evolution of the weak
structure into a series of sharp peaks corresponding almost exactly to the vibrational
progression in the lowest electronic state a
3
C of condensed CO [shown as recorded for a 10-
ML lm of pure condensed CO in Fig. 16(b)].
In their rst paper, Lepage et al. [37] demonstrated that the appearance of the CO
electronic state derives exclusively from the electron-induced fragmentation of condensed
methanol molecules. Assuming a uniform electron current density within the electron
beam, it can also be shown that for induced CO concentrations below 2%, an eective
cross section for CO production r
p
can be calculated via the formula
r
p
i
n
CO
S
0
n
0
I
0
t
14
where I
0
is the incident electron beam current and S
0
is its area; n
0
and n
CO
are the initial
number density of target molecules and the number density of CO molecules at time t,
respectively.
Figure 17 Total scattering cross section r
p
(left axis) and rate (right axis) for the production of CO
by electron impact on a 5-ML lm of methanol condensed on an Ar spacer as a function of the
incident electron energy. The dashed line is the intrinsic minimum rate of CO production due to the
measurement at E
i
=14 eV. (From Ref. 37.)
Fig. 17 exhibits the incident electron energy dependence of the r
p
and CO produc-
tion rate as a function of incident electron energy. The horizontal dashed line represents
the intrinsic minimum rate of CO production due to the measurement of the energy-loss
spectra at 14 eV. The CO production rate was found to increase linearly with the quantity
of deposited methanol indicating that the CO is generated by the interaction of an electron
at a single molecular site, rather than through reactions of fragment species with
surrounding (intact) molecules. The form of the CO yield function visible in Fig. 17 was
attributed to the formation of multiple transient anions at these low incident energies. In
addition to DEA via long-lived resonances, molecular dissociation is possible via shorter-
lived states that decay to neutral repulsive states of CH
3
OH. By comparison with H
ESD
yield functions [259] and vibrational excitation functions [116] for condensed CH
3
OH,
Lepage et al. ascribed the shoulder at 11.5 eV and broad maximum centered at 14.5 eV in
Fig. 17 to the . . .(6aV)
1
(3saV)
2
,
2
A,. . .(1a)
1
(3saV)
2
,
2
A, and . . .(5aV)1(3saV)
2
,
2
AV core-excited
electron resonances, which decay into their parent repulsive states. The rising signal above
19 eV was attributed to direct ionization of CH
3
OH.
The same experimental techniques were applied to measure eective cross sections
for the electron-induced production of CO from condensed acetone [38], which again was
attributed to the formation of TNI and their decay to neutral dissociative states. HREELS
measurements have also been used to study electron-induced degradation of cyclopropane
[260] and CH
3
Cl on graphite [261].
4. RESULTS FOR LOW-ENERGY ELECTRON INTERACTIONS WITH DNA
AND OTHER BIOMOLECULES
4.1. LEE Damage to Plasmid DNA
The DNA molecule is composed of two strands of repeated sugar-phosphate units
hydrogen-bonded together by the bases (adenine, thymine, guanine, and cytosine) which
are covalently linked to the sugar moiety of the backbone. Results obtained from electron
bombardment of solid lms of DNA and its constituents are presented in the following
sections. These latter include H
2
O, the bases, and the backbone dioxyribose analogs such
as tetrahydrofuran.
Damage to pure dry samples of supercoiled DNA has been induced by bombard-
ment with 3 eV to 1.5 keV electrons under a hydrocarbon-free 10
9
Torr residual
atmosphere [262265]. These experiments required the adoption of sample preparation
and analytical techniques [263] unlike those already described for simple atomic and
molecular solids. They are briey discussed here. Supercoiled plasmid DNA [pGEM
3Zf(), 3199 base pairs] is rst extracted from Escherichia coli DH5a, puried, and
resuspended in nanopure water into a clean N
2
-lled glove box, where the following
manipulations are performed. An aliquot of this pure aqueous DNA solution is deposited
onto chemically clean tantalum substrates held at liquid nitrogen temperatures, lyophi-
lized with a hydrocarbon-free sorption pump at 0.005 Torr, and transferred directly in a
UHV chamber without exposure to air. After evacuation for
f
24 hr, room-temperature
DNA solid lms of 5-ML average thickness and 6-mm diameter are irradiated with a
monochromatic LEE beam of the same diameter. Each target is bombarded for a specic
time at a xed beam current density (2.210
12
electrons sec
1
cm
1
) and E
i
. After 24 hr
under UHV, the DNA still contains 2.5 H
2
O molecules/base pair as structural water [266].
After bombardment, the DNA is analyzed by agarose gel electrophoresis and quantied as
supercoiled (undamaged), nicked circle (single strand breakSSB), full-length linear
(double strand breakDSB), and short linear forms [264]. By measuring the relative
quantities of the various forms of DNA in the sample as a function exposure to 10, 30, and
50 eV electrons, it was possible to obtain the total eective cross section (
f
410
15
cm
2
)
and eective range (
f
13 nm) for destruction of supercoiled DNA at these energies [263].
Such experiments also allowed the identication of the regime in which the measured
yields were linear to electron exposure. It is within this regime that the incident electron
energy dependence of damage to DNA was recorded more continuously between 3 and
100 eV [262,263,265]. The most striking observations were that (1) these yields did not
depend on the ionization cross section and (2) below 15 eV, they varied considerably with
E
i
. Above 20 eV, the yields of SSB and DSB did not exhibit pronounced energy variations
nor did they increase considerably with increasing energy.
The incident electron energy dependence of these yields below 20 eV are displayed in
Fig. 18 and show that LEE induce SSBs and DSBs, even at electron energies below the
ionization limit of DNA (
f
8 eV) [267]. Also, the damage is highly dependent on the initial
kinetic energy of the incident electron, particularly below 14 to 15 eV, where thresholds
near 3 to 5 eV and intense peaks near 10 eV are observed. The results shown in Fig. 18 can
be understood by investigating the fragmentation induced by LEEs to the various subunits
of the DNA molecule, including its structural water.
Figure 18 Measured quantum yields, per incident electron, (a) for the induction of DSBs, (b)
SSBs, and (c) loss of the supercoiled DNA form, in DNA solids by low-energy electron irradiation as
a function of incident electron energy; the curves are guides to the eye. (From Ref. 262.)
4.2. Electron-Stimulated Desorption from Water Ice Films
The damage induced by LEE impact on amorphous ice lms has been measured by
recording H
[223,268,269], H
2
[46,270], D(
2
S), O(
3
P), and O(
1
D
2
) [47,271] desorption yield
functions in the range 530 eV. Most of these functions exhibit resonance structures below
15 eV which are characteristic of TNI formation. From anion yields, DEA to condensed
H
2
O was shown to result principally into the formation of H
and the OH radical from

dissociation of the
2
B
1
state of H
2
O
located in the 79 eV region as shown in Fig. 19.

Smaller contributions from the
2
A
1
and
2
B
2
anionic states formed near 9 and 11 eV,
respectively [268,269], contribute to a lesser extent to the H
signal. At higher energies,

nonresonance processes such as DD lead to H
2
O fragmentation with the assistance of a
broad resonance extending from 20 to 30 eV [268,269]. In some of the water ice experi-
ments, the temperature of the substrate was modied before or after water condensation in
order to investigate the eects of morphology and porosity [44,223,269].
Figure 19 Dependence on E
i
of D
yield collected at various temperatures from a 20-bilayer

porous amorphous ice lms grown at 27 K. Individual scans are oset vertically for display and are
labeled with the temperature at which they were collected. (From Ref. 223.)
The temperature dependence of the D
signal from 20 bilayers of porous amorphous

ice, grown at 27 K [223], is shown in Fig. 19. Both the resonance energies and the ion yields
change with temperature. An analysis of the D
onset energy and the energy and intensity

of the low-energy resonance peak indicates that there is a break in this behavior at around
60 K. The peak intensity increases vefold between 27 and 60 K, remains roughly constant
between 60 and 100 K, and then more than doubles in going from 100 to 140 K. These
results were attributed to thermally induced movement of the hydrogen-bonding network
which changes the orientation of the surface molecules and the lifetimes of the predis-
sociative transient anions that lead to ESD.
Kimmel et al. measured the D
2
(X
1
A
g
+
), D(
2
S), O(
3
P
j=2,1,0
), and O(
1
D
2
) products
[47,271] desorbing from D
2
O multilayers (
f
20 nm) grown on a platinum(111) crystal at
88 K under conditions which are known to produce amorphous ice. The ice samples were
irradiated with a pulsed electron beam in an apparatus similar to the one shown in Fig. 2,
and the desorbing neutral products were ionized by laser resonance-enhanced multiphoton
absorption. State-specic time-of-ight distributions were obtained by varying the delay
time between the electron-beam pulse and the laser pulse. The D(
2
S) yield function
exhibited an apparent threshold at
f
6.5 eV followed by a rapid increase in signal until a
distinct plateau was reached for
f
14VE
i
V21 eV. The signal increased more gradually for
electron energies above 21 eV. The thresholds for the O(
3
P
2
) and O(
1
D
2
) signals also lay in
the range 6 to 7 eV, but the line shape of the yield function was featureless.
The low threshold energies for the production of D(
2
S), O(
3
P), and O(
1
D
2
) show the
importance of valence excited states in the ESD of neutral fragments [47]. The pathway for
D(
2
S) desorption probably involves D
2
O*D+OD. However, the thresholds for producing
O(
3
P
2
) and O(
1
D
2
), which are the same within experimental error, are lower than the 9.5-
and 11.5-eV thermodynamic energies required to produce O(
3
P
2
)+2D(
2
S) and O(
1
D
2
)+
2D(
2
S), respectively. The low threshold values therefore indicate that the formation of
O(
3
P
2
) and O(
1
D
2
) must occur by a pathway which involves simultaneous formation of D
2
.
Kimmel et al. have in fact reported [46] a threshold for the production of D
2
from D
2
Oice at
f
6 to 7 eV, which supports this conclusion. Above the ionization threshold of amorphous
ice, these excited states can be formed directly or via electronion recombination.
4.2. Anion Electron-Stimulated Desorption from Thin Films of
Deoxyribose Analogs
To understand how breaks may occur via direct LEE impact on subunits of the backbone
of DNA, ESD experiments were performed with solid lms of the sugar-like analogs
[272,273] tetrahydrofuran (I) and its analogs 3-hydroxytetrahydrofuran (II) and a-
tetrahydrofuryl alcohol (III) (structures shown in Fig. 20).
The H
ion yields desorbed by the impact of 120 eV electrons on 10-ML lms of I,

II, and III are shown in Fig. 20. The curves are characterized by an onset at 6.0, 5.8, and
6.0 eV and a yield maximum centered at 10.4, 10.2, and 10.0 eV for I, II, and III, re-
spectively. A second feature is also observed in the H
yield function for II; it appears as a

shoulder on the low-energy side of the 10-eV peak and is characterized by a sharp onset
and a peak maximum near 7.3 eV.
All features below 15 eV in Fig. 20 are characteristic of DEA to I, II, and III. The
monotonic rising signal in the H
yield with an energetic threshold near 14.5 eV is

characteristic of nonresonant DD of CH bonds in I, II, and III; it could also partially
arise from DD of the OH bond in II and III. However, the broad feature centered around
22 eV has been attributed to DEA and/or resonance decay into an electronically excited
state dissociating into H
and the corresponding cation. The formation of H
via DEA
from I, II, and III has been discussed in detail by Antic et al. [272,273]. These authors
considered the possibility of H
arising from dissociation of the tetrahydrofuran ring, the

OH, and the CH
2
OH group. Other decay channels of the transient anions could result in
the formation of larger anion fragments, such as OH
and CH
2
OH
, and compete with

H
production, but these heavier ions were not observed to desorb. Typically, large mass
fragments do not possess sucient kinetic energy to escape induced polarization and thus
remain trapped within the lm [147]. Owing to the strong similarity of the H
desorption
proles for I, II, and III, these authors concluded that the majority of the anion yield for
all three systems arises from at least one transient anion associated with electron attach-
ment to the furan ring and located near 10 eV. Considering the largely Rydberg character
of the excited states in I near the energy range of the observed resonance, they further
suggested that this resonant state is of the core-excited type, possibly with dissociative
valence r* congurational mixing.
4.4. Anion Electron-Stimulated Desorption from Thin Films of DNA Bases
Electron impact dissociation of DNA bases has been investigated in the gas [274] and the
condensed phase [26,39,275]. In both phases, a large variety of stable anions is produced via
DEAto the bases for electron energies below30 eV. The anions H
, O
, CN
, CH
, OCN
,
and OCNH
2
were observed from gaseous thymine, whereas electron impact on gaseous

Figure 20 Comparisons of H
ESD yields produced by impact of 0- to 40-eV electrons on 6-ML-

thick lms of the DNA backbone sugarlike analogs tetrahydrofuran (I), 3-hydroxytetrahydrofuran
(II), and a-tetrahydrofuryl alcohol (III). The smooth solid lines serve as guides to the eye. (From
Ref. 272.)
cytosine resulted in the formation of the anions H
, C
, O
, and/or NH
2
, CN
, OCN
,
C
4
H
5
N
3
, and/or CH
4
N
3
O
and C
3
H
3
N
2
[274]. All four bases were investigated in the form

of thin multilayer lms held at room temperature, but fewer anions of dierent masses were
measured than in the gas phase [26,275]. The dierence is principally due to the inability of
the heavier anions to overcome the polarization potential they induce in the lm, causing
them to remain undetected in the target [147]. In fact, only the light anions H
, O
, OH
,
CN
, OCN
, and CH
2
were found to desorb by the impact of 530 eV electrons on the

physisorbed DNA bases adenine, thymine, guanine, and cytosine via either single or
complex multibond dissociation [275]. As an example, the CN
yield functions produced

by 320 eV electron impact on thin lms of each of the four bases are shown in Fig. 21. All
yield functions exhibit maxima whichare characteristic of DEAtothe bases. Whereas anions
i
of CN
ion yields desorbed under 500-nA electron bombardment of

8-ML-thick lms of (a) adenine, (b) thymine, (c) guanine, and (d) cytosine. (From Ref. 275.)
such as H
can be induced via a simple bond cleavage fromthe bases, the production of CN
occurs under more complex ring dissociation. It shouldbe noted that the extractionof a CN
anion from any DNA base must involve more than a single bond cleavage. In other words,
during the lifetime of the negative ion, not only exocyclic single bond occurs, but also
complex endocyclic multibond cleavages are involved via most likely either stepwise [276] or
rearrangement reactions [277]. The similarity of the CN
, OH
, and O
ion yield functions

with resonant peaks at 9.0 and 10 eV from guanine or cytosine and thymine lms,
respectively, observed by Abdoul-Carime et al. [275], suggests that they arise from the
formation of the same excited isocyanic anion intermediate (OCNH)*
, via closely lying but

distinct resonances, i.e., (G
, Cy
, or T
)R+(OCNH)*
, where Rrepresents the remaining

radical; then (OCNH)*
further undergoes fragmentation into dierent possible dissocia-

tive channels: CN
+OH, OH
+CN, or O
+CNH.
4.5. Neutral Species Electron-Stimulated Desorption from Short Single
DNA Strands
In recent experiments, the damage produced by LEE impact on short single strands of
DNA was measured by ESD. Work in this area has been largely performed by Dugal et al.
[278,279] and Abdoul-Carime et al. [280283], who measured the yields of neutral
fragments induced by 130 eV electron impact on oligonucleotides consisting of 6 to 12
base units. The oligomers were chemisorbed on a gold surface via sulfur bounding. Their
results showed that LEE impact dissociation of DNA bases led to desorption of CN,
OCN, and/or H
2
NCN neutral species as the most intense observable yields. No sugar
moieties were detected; neither phosphorus-containing fragments nor entire bases were
observed to desorb. These results were obtained from mass spectrometric measurements of
the residual atmosphere near the target during its bombardment in UHV by a high current
10
8
A electron beam. Fig. 22 presents the electron energy dependence of neutral CN
(solid square) and OCN (and/or H
2
NCN) (open circle) fragments desorbed per incident
electron from oligomers consisting of nine bases [281]. The upper, middle, and lower
panels show the results from oligonucleotides consisting of nine cytosine bases, Cy
9
, six
cytosine bases and three thymine bases, Cy
6
T
3
, and six cytosine bases and three
bromouracil bases, Cy
6
BrU
3
, respectively. The latter base is not naturally found in
DNA but can be substituted for thymine and be incorporated into cellular DNA to
enhance the therapeutic eects of high-energy radiation [284]. Above 20 eV in Fig. 22, the
neutral fragment production increases linearly with the E
i
, which is indicative of molecular
fragmentation governed mostly by nonresonant DD and/or dissociative ionization of the
bases. Below 20 eV, base fragmentation may involve excitation to dissociative electronic
neutral states and DEA [278280]. The curves in Fig. 22 present broad peaks extending
from 7 to 15 eV for all oligomers. At these high energies, these broad maxima are likely to
reect the formation of core-excited resonances that are dissociative in the Franck
Condon region. This interpretation is supported by: (1) the electron energy losses in solid
phase DNA bases [285] in the 715 eV range, which are attributed to either p or r orbitals;
and (2) observation of resonant formation CN
, O
, and/or NH
2
and H
at 910, 79,
and 1213 eV, respectively, in electron-stimulated desorption yields from thin lms of
DNA bases [26,275]. Moreover, the threshold of neutral species production observed at 5
eV coincides with the threshold for electronic excitations, suggesting that the onset of the
nucleic acid fragmentation involves dissociative electronic transitions.
An extra peak is observed at 3 eV for BrU-substituted oligonucleotides in the inset at
the bottom of Fig. 22. Since this peak lies at an energy too low to involve electronically
excited states, it probably arises from the formation of a shape resonance consisting of the
BrU molecule in the ground state with an electron occupying a usually unlled orbital. In
XPS [39] investigations of LEE-induced damage to Bromouracil, it was found that Br
production below 5 eV involves resonant electron capture by BrU followed by dissociation
into a uracil-yl radical (U).
4.6. Discussion
In previous sections, we have seen that the dependence on E
i
of damage to elementary
constituents of DNA, probed in the form of desorbed anions, exhibits strong variations
i
of neutral CN (solid square) and OCN (and/or H
2
NCN) (open circle)
fragment desorption yields per incident electron from Cy
6
-(Cy)
3
oligos (upper panel), Cy
6
-(Th)
3
oligos (middle panel), and C
6
-(BrU)
3
oligos (bottom panel). The spread in the data is estimated to be
20%. (From Ref. 281.)
due to electron resonances. Maxima in the anion desorption yields are due to DEA, while
those appearing in the neutral radical yields may result from either DEA or the decay of a
transient anion into an electronically excited state which is dissociative. Thus from these
data, it becomes quite obvious that the strong energy dependence of the DNA strand
breaks below 15 eV in Fig. 18 can be attributed to the initial formation of transient
anions, decaying into the DEA and/or dissociative electronic excitation channels. How-
ever, since the basic DNA components (i.e., the sugar and base units and structural H
2
O)
can all be fragmented via DEA between 5 and 13 eV, it is not possible to unambiguously
attribute SSB and DSB to the initial dissociation of a specic component. For example,
the maximum in the SSB yield lying near 8 eV is very close to the maximum in H
+OH
production from H
2
O, but the DNA bases also produce H
and the corresponding

radical with high eciency near 9 eV. What appears to be more convincing is the
coincidence in the 10-eV peak in H
production in Fig. 20 from tetrahydrofuran and its

analogs, with that in the DSB yield seen in Fig. 18. This is not surprising since two events
are necessary to create a DSB, and the probability for such breaks is likely to be larger
when the rst hit breaks a strand (i.e., breaks the sugar-phosphate backbone). Another
interesting aspect of the DSB yield curve is the absence of damage induced by direct
(nonresonant) electronic transitions. Indeed, the two points in Fig. 18 around 14 and 15
eV lie at the zero base line, indicating that below
f
16 eV, DSB occurs exclusively via the
decay of transient anions. These observations suggest that below 16 eV, DSB occurs via
molecular dissociation on one strand initiated by the decay of a transient anion, followed
by reaction of at least one of the fragments on the opposite strand. This hypothesis is
further supported by the observation of electron-initiated fragment reactions (such as
hydrogen abstraction, dissociative charge transfer, atom and functional group exchange,
and reactive scattering) occurring over distances comparable to the DNAs double-strand
diameter (
f
2 nm) in condensed lms containing water or small linear and cyclic
hydrocarbons [246,257].
5. APPLICATIONS IN OTHER FIELDS
5.1. Dielectric Aging and Breakdown
Electrical insulation is often exposed to stresses which with time reduce the insulating
properties of the dielectric material. This deterioration is referred to as aging. Aging
stresses include temperature, applied voltage, and mechanical force; these are aected by
environmental factors such as the presence of water, oxygen, corrosive materials, and
radiation. While electronic aging (i.e., that due to the application of high electric elds)
produces macroscopic modications of dielectric materials, it is probably initiated at the
nanoscale level in the early life of the material under stress [72,286,287]. The accumulated
space charge is both a precursor to and a contributing cause of electrical breakdown
[72]. In fact, it has been shown that LEEs play a signicant role in the processes leading to
the breakdown of the dielectric materials used to insulate high-voltage power cables [162].
These so-called hot electrons can be released into the conduction band following energy
absorption from phonons in the dielectric or from external particles penetrating the solid
(e.g., UV photons and g-rays) [7,162]. Despite being accelerated by the ambient electric
eld, initial hot electrons would rarely gain sucient energy to break molecular bonds
before becoming trapped. However, those accelerated in cavities of micrometer diameters
could attain the higher kinetic energies of several eV, required to rupture molecular bonds
and hence contribute to the aging process. Consequent changes in chemical nature or
excessive charge accumulation at specic locations would eventually cause electrical
breakdown [7,162].
To better understand the mechanisms responsible for charge accumulation in
dielectrics, the technique for measuring induced charge in millimeter-thick molecular
solids described in Sec. 3.1.2 has been applied to macroscopic samples of cross-linked
polyethylene (XPLE) cut from industrial power lines [32]. As an example of the type of
information obtainable with the new instrument, Fig. 23 shows both the instantaneous
trapping probability DQ
t
/Q
0
, measured with the electrometer (black dots), and DV/Q
0
(open circles), obtained with the Kelvin probe, as functions of E
i
. A geometrical factor a of
1.3, consistent with the experimental geometry [32], is required to bring these two type of
data into quantitative agreement. The data presented in Fig. 23 reveal that charge trapping
is most ecient at very low energies, as is evidenced by the peak near 1 eV. A smaller,
second peak is observed near 10 eV. The negative data values obtained between 15 and 25
eV indicate that over this range, the sample charges positively with respect to the
unbombarded sample, taken as the zero potential reference.
From comparison with the results of charge trapping and anion ESD experiments on
pure and doped n-hexane lms [32] (see as an example Fig. 13), it has been suggested that
negative charging between 7 and 15 eV in XPLE is dominated by DEA to alkane chains.
In contrast, charging below 5 eV is likely to be associated with molecular impurities
(water, O
2
, and antioxidant additives) since pure alkane molecular solids are unable to
trap electrons at these energies (Fig. 13).
5.2. Electron Beam and Nanolithography
Intense interest exists in producing nanometer-scale structures for new and existing
applications in the elds of electronics, optics, and molecular electronics. Among the
most promising approaches to producing submicrometer structures are electron beam
Figure 23 The trapping probability (DQ/Q
0
) and variation in surface potential per incident charge
DV/Q
0
, as functions of incident electron energy for the 115-mm-thick cross-linked polyethylene
(XLPE) sample. (From Ref. 32.)
lithography and its newer ospring, scanning-probe lithography, in which a scanning
tunneling microscope (STM) or an atomic force microscope is used to deliver (or induce) a
localized electron current [288,290].* One limitation to producing nanoscale etching masks
is the large size of molecules used in the standard polymeric resists. Considerable interest
lies then in producing new resists from smaller molecules and/or self-assembled mono-
layers [9]. In other research, an STM is used to produce a resist by inducing reactions
between a substrate and adsorbed molecules, for example, the oxidation of Si(111) and
(100) surfaces under ambient conditions [290] or that between chlorobenzene and Si(111)
[291]. Low-energy electrons are present in such situations, either as a primary source of
energy or as secondary electrons produced by high-energy electron beams. Therefore the
electron-scattering processes already described should play a role in the electron-induced
modication and/or chemical changes. Indeed, LEEs via DEA or other processes might be
usefully employed to induce particular chemical reactions.
y
In this case, it would appear
advantageous to study the electron energy dependence of any chemical changes in the
resist material.
As an example, XPS has been used to analyze modications induced by 2 to 20 eV
electrons incident on a hydrogen-passivated and sputtered Si(111) surface, onto which had
been physisorbed thin lms of H
2
O [293,294] and CF
4
[295]. In both cases, following the
electron-induced dissociation of the molecular adsorbate, a new XPS signal associated
with the chemisorption of either O or F onto the Si surface was observed and an eective
cross section for chemisorption was then calculated. This cross section for electron-
induced chemisorption of oxygen from an H
2
O bilayer onto a hydrogen-passivated Si(111)
surface is shown in Fig. 24 as a function of E
i
[293,294]. The low energetic threshold for
the chemisorption process (i.e., 5.2 eV) has been interpreted as due to the formation of OH
via the DEA process
H
2
OX e
X H
2
O
2
B
1
;
1
A
1
! H
2
S
0
OH
2
P
1
and its subsequent reaction with the surface, viz.,

Si
3
Si H OH ! Si
3
Si OH H:
The chemisorption process has its maximum cross section at
f
11 eV in contrast with
cross sections for the radiolysis of bulk ice. This dierence was understood as being
dependent on the selective quenching of dissociative electronic states of water due to the
resonant charge exchange between the substrate and adsorbate and the absence of multiple
inelastic scattering in the H
2
O bilayer on Si(111).
A similar XPS study has been performed for
f
1 ML of CF
4
deposited onto the same
hydrogen-passivated Si substrate [295] and clearly demonstrates that chemisorption of the
F-containing species is dependent on the DEA reactions
CF
4
e
! CF
4
! F
CF
3
CF
4
e
! CF
4
! F CF
3
as an initial step for further reactions of fragments with the Si substrate.
* For a review, see Ref. 289.
y
For example, Ref. 292.
5.3. Atmospheric Processes
In a recent review, Madey et al. [296] describe how in interplanetary space, energetic
photons, ions, and electrons from the solar wind, together with galactic and extragalactic
cosmic rays, constantly bombard surfaces of planets, planetary satellites, dust particles,
comets, and asteroids. The authors suggest that much can be learned about the tenuous
atmospheres surrounding these bodies by studying the interactions of energetic particles
producing LEE secondary electrons with the molecular constituents of their surfaces. For
example, Sieger et al. [10] have demonstrated the production of O
2
from ice lms by
electron impact at 200 eV and have posited this mechanism as a source of O
2
in the
atmospheres of Ganymede and Europa.
The presence of ionizing radiation in the upper regions of the earths atmosphere and
the realization that atmospheric chemistry can occur on the surface of ice and dust
particles have lead many authors to study on the interaction of LEEwith molecular solids of
ozone [203], HCl [236], and halogen-containing organic compounds [176,177,195197,199
202,205,214,217,224234] in aneort toshed newlight onthe problemof ozone depletion. In
a recent series of experiments, Lu and Madey [297,298] found that the F
and Cl
yields
Figure 24 Experimental cross sections for the electron-induced oxidation of the a-H:Si(111)
surface as a function of incident electron energy. The solid line is drawn to guide the eye. (From Ref.
294.)
produced by the impact of 250-eVelectrons on CF
2
Cl
2
adsorbed on a metal Ru surface were
enhanced by several orders of magnitude when co-adsorbed with polar molecules such as
H
2
O and NH
3
. Subsequent charge-trapping measurements by Lu and Sanche [235] also
display an enhancement in stable anion formation at electron impact energies near 0 eV. Fig.
25(a) shows charging coecient A
s
(E
i
) for 10 ML of Kr deposited on Pt foil (solid triangles)
and that for 0.1 ML of CF
2
Cl
2
deposited on the Kr surface (open squares). These results can
be compared to those for 5 MLof H
2
Oon 10 MLof Kr and for 0.1 MLof CF
2
Cl
2
on 5 MLof
H
2
O on Kr [solid circles and open diamonds, respectively, in Fig. 25(b)]. In contrast to pure
Kr lms, which do not trap electrons, both H
2
O- and CF
2
Cl
2
-covered lms show signicant
charging. The results for H
2
O are similar to earlier measurements [222,223]. Those for
CF
2
Cl
2
correspond to a maximum trapping cross section of 1.410
15
cm
2
[235] near 0 eV,
attributed to charge stabilization as Cl
, via the previously identied DEA reaction

CF
2
Cl
2
+e(
f
0 eV)!CF
2
Cl+Cl
[299], and here enhanced by approximately an order of

magnitude by the eects of surface polarization (e.g., Ref. 226). However, when the same
quantity of CF
2
Cl
2
is deposited on the H
2
O, the charging coecient per CF
2
Cl
2
molecule at
Figure 25 Charging coecient A
s
as a function of E
i
for (a) 10 ML Kr condensed (solid triangles)
and 0.1 ML CF
2
Cl
2
on 10 ML Kr (open squares); (b) 5 ML H
2
O on 10 ML Kr (solid circles) and 0.1
ML CF
2
Cl
2
on 5 ML H
2
O on 10 ML Kr (open diamonds). (From Ref. 235.)
0 eV increases approximately a factor 10 to 1.310
14
cm
2
. A further order of magnitude
enhancement is observed for CF
2
Cl
2
on NH
3
[235].
It has been argued [235] by analogy with the case of molecules adsorbed on glassy n-
hexane [232] that this enhancement is due to the electron transfer to CF
2
Cl
2
of an electron
previously captured in a precursor state of the solvated electron in the water layer, which
lies at and just below the vacuum level [300,301] and the subsequent. Similar results have
been reported for HCl adsorbed on water ice [236]. It has been proposed that enhanced
DEA to CF
2
Cl
2
via electron transfer from precursor-solvated states in ice [235] may
explain an apparent correlation between cosmic ray activity (which would generate
secondary LEE in ice crystals) and atmospheric ozone loss [11]. The same electron transfer
mechanism may contribute to the marked enhancement in electron, and x-ray-induced
dissociation for halo-uracil molecules is deposited inside water ice matrices [39].
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10
ElectronIon Recombination in Condensed
Matter: Geminate and Bulk Recombination
Processes
Mariusz Wojcik
Technical University of Lodz, Lodz, Poland
M. Tachiya
National Institute of Advanced Industrial Science and Technology (AIST),
Tsukuba, Japan
S. Tagawa
Osaka University, Osaka, Japan
Y. Hatano
Tokyo Institute of Technology, Tokyo, Japan
SUMMARY
A survey is given of the theoretical and experimental studies of electronion recombina-
tion in condensed matter as classied into geminate and bulk recombination processes.
Because the recombination processes are closely related with the magnitudes of the elec-
tron drift mobility, which is largely dependent on molecular media of condensed matter,
each recombination process is discussed by further classifying it to the recombination in
low- and high-mobility media.
1. THEORY OF ELECTRONION RECOMBINATION IN CONDENSED
MATTER
1.1. Introduction
Ionization of atoms or molecules is the main primary event induced by the interaction of
radiations with condensed matter. The charged species produced by ionization, if not
removed from the irradiated system, will naturally tend to recombine. The conventional
theories of recombination treat the transport and reactions of charged species only after
the electrons ejected from atoms or molecules become thermalized by dissipating their
initially high kinetic energies to the surrounding medium and form a spatial distribution
around their parent cations. The thermalization in condensed phases is fast and is usually
completed on the timescale shorter than picoseconds. Following thermalization, electrons
and their parent cations perform a diusive motion in each others Coulomb eld, and
may react on encounter to form neutral products. This phase of recombination, in which
the ionized system may be described as a collection of independent electroncation pairs, is
called geminate recombination. In the course of this process, a fraction of electrons may be
separated from their parent cations far away, so that the Coulomb interaction between the
electron and the cation becomes very weak and they may be considered as free charges.
Then, the initial correlations within the geminate pairs are lost, and the spatial distribu-
tions of positive and negative charges in the irradiated system become independent of each
other and uniform. This sets the initial conditions for the next stage of recombination,
called bulk recombination, in which all charges in the system will nally be neutralized in a
homogeneous, second-order process.
Dividing the electronion recombination processes into two phases, well separated
in the time domain, has provided a convenient basis for constructing theoretical models,
in which the geminate phase is usually characterized by the pair reaction (or escape)
probability, and the bulk phase by its reaction rate constant. However, one should realize
that in real systems the general picture of the recombination processes is not in all cases
so simple. The spatial distributions of ionization events in tracks of radiations are usually
not homogeneous. Ionizations may occur in clusters (often called spurs or blobs) or form
columns (sometimes called short tracks), where the distances between neighboring cat-
ions are shorter than the average electron thermalization distance. In such a case, in
addition to geminate recombination between electrons and their parent cations, cross-
recombination between electrons and nonparent cations belonging to the same cluster or
column is also possible. Another complication arises from the fact that in many systems,
the recombination processes are intercepted by chemical reactions involving electrons or
cations.
The course of the recombination processes in a particular system depends on several
factors. One of the most important ones is the polarity of the system. Both geminate and
bulk recombination processes are strongly inuenced by the Coulomb attraction between
electrons and cations, and the range of this interaction in condensed matter is determined
by the dielectric constant e. The range of the Coulomb interaction in a particular system
is usually represented by the Onsager radius, r
c
, which is dened as the distance at which
the electrostatic energy of a pair of elementary charges falls down to the thermal level
k
B
T.
r
c

e
2
ek
B
T
1
Here e is the electron charge, k
B
is the Boltzmann constant, and T is temperature. The
value of r
c
in nonpolar liquids at room temperature may be as high as
f
30 nm, while in
water it is only 0.7 nm. Because the electron thermalization distances are usually on the
order of a few nanometers, the eect of the Coulomb attraction between the ionization
products in water will be much weaker than that in, e.g., liquid hydrocarbons. This will
result in much lower probabilities of geminate recombination in polar liquids compared
to those in nonpolar ones.
Another factor that strongly aects the recombination processes is the mobility of
charges, or, more generally, the mechanism of charge transport in a particular system. It is
normally assumed that the transport of both electrons and cations may be described as
ideal diusion. This assumption is justied in most polar systems, as well as in a part of
nonpolar ones. However, in a number of nonpolar systems, usually characterized by high
electron mobility, it is more appropriate to describe the electron motion as ballistic
rather than Brownian. The transport of positive charges may be, in some cases, better de-
scribed as a resonant charge hopping rather than the diusion of cations. Dierent theo-
retical approaches are needed to describe the recombination processes in high-mobility
systems.
The electronion recombination processes are also strongly dependent on the type of
radiations that ionize a particular system. As it was already mentioned, track eects
determine the initial spatial distributions of cations and electrons in irradiated systems.
In the following sections, we present the most important theoretical results concern-
ing the electronion recombination in condensed matter. In Sec. 10.1.2, we concentrate on
the geminate recombination, and in Sec. 10.1.3 on the bulk recombination. In both cases,
we start with the diusion theory (Secs. 10.1.2 Diusion-Controlled Geminate Ion
Recombination and 10.1.3 Diusion-Controlled Bulk Ion Recombination), and
present its results for the escape probability in the geminate phase, and the recombination
rate constant in the bulk phase. We also discuss transient eects and the eects of an
applied electric eld on the recombination processes considering their experimental
importance. In the case of the geminate recombination, we include the theory of electron
scavenging and a brief discussion of the multipair eects in radiation tracks. Theoretical
studies of the recombination processes in high-mobility systems require an approach that
is quite dierent from that used in the theory of diusion-controlled recombination.
Therefore we discuss the recombination processes in high-mobility systems in separate
subsections [Secs. 10.1.2 (Geminate Ion Recombination in High-Mobility Systems) and
10.1.3 (Bulk Ion Recombination in High-Mobility Systems)].
1.2. Geminate Ion Recombination
Diusion-Controlled Geminate Ion Recombination
The central problem in the theory of geminate ion recombination is to describe the relative
motion and reaction with each other of two oppositely charged particles initially separated
by a distance r
0
. If we assume that the particles perform an ideal diusive motion, the time
evolution of the probability density, w(r,t), that the two species are separated by r at time t,
may be described by the Smoluchowski equation [1,2]
Bwr;t
Bt
D j
2
wr; t
1
k
B
T
jwr; tVr
_ _
2
where D is the sum of the diusion coecients of the two particles and V(r) is the
interaction potential. The initial condition is given by
wr; 0
1
4pr
2
0
dr r
0
3
The probability density w(r,t) contains the complete information about the behavior of the
geminate pair. However, it is dicult to solve Eq. (2) in most cases of interest. Moreover,
the probability density w(r,t) itself is usually experimentally unobservable. The quantities
of greater practical importance are the pair survival probability dened as
Wt
_
wr; tdr 4
and its long-time limit
u lim
t!l
Wt 5
The latter quantity is called the escape probability, and describes the probability that the
two oppositely charged particles of the geminate pair will never recombine with each other
and become free ions.
By introducing an equation adjoint to Eq. (2), one can derive the following equation
for the pair survival probability [3]
BW
Bt
D j
2
r
0
W
1
k
B
T
j
r
0
Wj
r
0
V
_ _
6
where the space derivatives are the ones with respect to the initial separation r
0
. The escape
probability is shown [3] to satisfy the following equation by taking the limit of t!l in
Eq. (6)
j
2
r
0
u
1
k
B
T
j
r
0
uj
r
0
V 0 7
For the Coulomb potential given by
Vr
e
2
er
k
B
T
r
c
r
8
Eq. (7) may be written in the spherical coordinates as
d
2
u
dr
2
0
2
r
0
r
c
r
2
0
_ _
du
dr
0
0 9
The escape probability satises the following boundary condition at innity
ur
0
!l 1 10
In the equations written so far, the reaction between the particles of the geminate pair is
not accounted for. This can be performed by introducing a boundary condition at a
distance R, which is called the reaction distance. If the reaction on encounter is very fast,
one can use the totally absorbing boundary condition
wR; t 0 11a
Equation (11a) is sometimes called the absorption boundary condition. This boundary
condition is equivalent to the following boundary condition on the escape probability [4]
uR 0 11b
By solving Eq. (9) subject to boundary conditions (10) and (11b), the escape probability
for the totally diusion-controlled geminate ion recombination is calculated as
ur
0

exp
r
c
r
0
_ _
exp
r
c
R
_ _
1 exp
r
c
R
_ _ 12
Equation (12) is derived on the assumption of an instantaneous reaction of the opposite
ions once they approach each other to the distance R. However, in many real systems, the
rate of the reaction at the reaction distance is comparable to, or even slower than, the
diusive ux of the ions toward each other. This eect can be taken into account by
modifying the boundary condition at the reaction distance R. Instead of the totally
absorbing boundary condition (11a), one can use a partially reecting boundary condition
in the form [5]
D
Bwr; t
Br

wr; t
k
B
T
BVr
Br
_ _
rR
pwR; t 13a
where the left-hand side represents the ux of particles through the reaction surface, and
the parameter p is a measure of the intrinsic rate constant at the reaction distance.
Equation (13a) is sometimes called the radiation boundary condition. This boundary
condition leads to the following boundary condition on the escape probability [3]
D
Bur
0
Br
0
_ _
r
0
R
puR 13b
In the limit p!l, Eqs. (13a) and (13b) reduce to Eqs. (11a) and (11b), respectively. The
solution of Eq. (9) subject to the boundary conditions (10) and (13b) is given by [3]
ur
0

exp
r
c
r
0
_ _
1
Dr
c
pR
2
_ _
exp
r
c
R
_ _
1 1
Dr
c
pR
2
_ _
exp
r
c
R
_ _
14
This expression characterizes the escape probability for the partially diusion-controlled
geminate ion recombination.
In the case where the reaction distance may be assumed much shorter than the
range of the Coulomb interaction (R<<r
c
), Eq. (14) reduces to the well-known Onsager
formula [2]
ur
0
exp
r
c
r
0
_ _
15
This simple expression, which gives the probability that a pair of charges initially separated
by r
0
and performing a diusive motion in the mutual Coulomb eld will escape
recombination, has found numerous applications in various elds of physics and chemistry.
Another method of accounting for the reaction between the electron and the ion,
instead of imposing a specic boundary condition, is to introduce a sink termk
r
(r)w(r,t)
on the right-hand side of Eq. (2), where k
r
(r) is a rst-order rate constant [6]. This
approach is more general than that using the totally absorbing or the partially reecting
boundary conditions, in a sense that it is applicable to the case where the reaction occurs
over a range of distances. Moreover, it does not even require introducing the reaction
distance, which is a quantity dicult to dene in a real system. If the sink term is used to
represent the reaction, the escape probability satises
D
d
2
u
dr
2
0
2
r
0
r
c
r
2
0
_ _
du
dr
0
_ _
k
r
r
0
ur
0
0 16
When the reaction is represented by a sink term, a reective boundary condition must be
imposed at a contact distance d. This boundary condition leads to the following boundary
condition on the escape probability
Bur
0
Br
0
_ _
r
0
d
0 17
The solution of Eq. (16) depends on the assumed rate constant. In many cases, an
exponential form of the rate constant k
r
(r)
f
exp(ar), where a is a parameter, provides a
realistic model of the reaction. Unfortunately, it is usually not possible to nd simple
analytical solutions of Eq. (16), and the equation has to be numerically solved [7].
We have derived the escape probability for a pair of charges initially separated by a
given distance r
0
for various cases. However, in real systems, the electron thermalization
distance is distributed. If we denote the distribution of thermalization distances by f(r), the
total averaged escape probability, u
tot
, can be calculated from
u
tot

_
l
0
urfrdr 18
The exact form of f(r) is usually unknown, and the electron thermalization in irradiated
systems still remains a subject of both theoretical and experimental scrutiny. Often, f(r) is
approximated by a simple analytical expression, e.g., the exponential distribution
fr; r
0

1
r
0
exp
r
r
0
_ _
19
or the Gaussian distribution
fr; r
0

4r
2
p
p
r
3
0
exp
r
2
r
2
0
_ _
20
where r
0
is a parameter.
One of the most important experimental methods of studying the electronion
recombination processes in irradiated systems are measurements of the external electric
eld eect on the radiation-induced conductivity. The applied electric eld is expected to
increase the escape probability of geminate ion pairs and, thus, enhance the number of free
ions in the system, which will result in an enhanced conductivity.
The escape probability of an electron in an external electric eld F can generally be
obtained by solving Eq. (7) or (16) with the potential energy V given by
Vr; #
e
2
er
eFr cos # 21
Here # is the polar angle. We assume that the eld is directed along #=p. The boundary
condition at innity is given by Eq. (10), and the reaction may be described either by a
specic boundary condition at the reaction distance [Eq. (7)], or by a sink term [Eq. (16)],
as discussed before.
The solution of Eq. (7) with the potential energy described by Eq. (21), for the
boundary condition (11b) with R=0, was found by Onsager [2]. His result is given by
ur
0
; #; F exp
_
br1 cos #
_
l
r
c
=r
J
0
2
_
br1 cos #s
1=2
_ _
e
s
ds 22
where b=eF/2k
B
T and J
0
is a zeroth-order Bessel function of the rst kind. Because in real
systems, the angular dependence of the escape probability is usually unobservable, the
quantity that is experimentally more signicant is the escape probability u(r
0
,F ) averaged
over the polar angle #. Although no closed solution for u(r
0
,F ) is available, the eld
dependence of the angle-averaged escape probability can be described by an innite series
representation [8]
ur
0
; F expa b
1
b
l
l 1
l
b
a
_ _
l=2
I
l
2
ab
p
_ _
23
where a=r
c
/r
0
, b=eFr
0
/k
B
T, and I
l
are modied Bessel functions. A couple of dierent
series representations of u(r
0
,F ) are also available [9,10].
It can be shown that the expansion of u(r
0
,F ) up to the rst order in F gives the
expression
ur
0
; F exp
r
c
r
0
_ _
1
eFr
c
2k
B
T
_ _
24
This equation shows that at low electric elds, the escape probability is a linear function of
F, and the slope-to-intercept ratio of this dependence is given by er
c
/2k
B
T. It is worth
noting that this ratio is independent of r
0
. Therefore plots of u( F )/u(0) vs. F may be used
to test the applicability of the presented theory to describe real systems, even if the dis-
tribution of electron thermalization distances is unknown.
Calculation of the electric eld dependence of the escape probability for boundary
conditions other than Eq. (11b) with R=0 poses a serious theoretical problem. For the
partially reecting boundary condition imposed at a nonzero R, some analytical treat-
ments were presented by Hong and Noolandi [11]. However, their theory was not de-
veloped to the level, where concrete results of u(r
0
,F ) for the partially diusion-controlled
geminate recombination could be obtained. Also, in the most general case, where the
reaction is represented by a sink term, the analytical treatment is very complicated, and the
only practical way to calculate the eld dependence of the escape probability is to use
numerical methods.
In Fig. 1, we plot the electron escape probability of geminate ion pairs as a function
of the external electric eld. The solid lines show the results calculated using Eq. (23) for
various initial separations r
0
. The broken lines represent the results of u(r
0
,F ) obtained by
numerically solving Eq. (16), which includes the sink term k
r
u to represent the reaction
[12]. The rate constant k
r
is assumed in the form k
r
(r) =Aexp[a(rd )], and the
parameters are chosen in such a way that the recombination is partially diusion-
controlled. We see that the electric eld dependence of the escape probability in the
partially diusion-controlled recombination is signicantly dierent from that in the
totally diusion-controlled recombination. This indicates that the eects due to the nite
rate of the reaction cannot be neglected in analyzing experimental data. We should also
bear in mind that in real systems the electron thermalization distance r
0
is distributed. To
calculate the escape probability for a given thermalization distance distribution f(r), one
has to average u(r,F ) over f(r).
In the preceding part of this section, we have concentrated on the electron escape
probability, which is an important quantity in the geminate phase of recombination, and
can be experimentally observed. However, modern experimental techniques also give us a
possibility to observe the time-resolved kinetics of geminate recombination in some
systems. Theoretically, the decay of the geminate ion pairs can be described by the pair
survival probability, W(t), dened by Eq. (4). One method of calculating W(t) is to solve
the Smoluchowski equation [Eq. (2)] for w(r,t) and, then, to integrate the solution over the
space variable. Another method [4] is to directly solve Eq. (7) under relevant conditions.
The analytical solution of the Smoluchowski equation for a Coulomb potential has
been found by Hong and Noolandi [13]. Their results of the pair survival probability, ob-
tained for the boundary condition (11a) with R = 0, are presented in Fig. 2. The solid lines
show W(t) calculated for two dierent values of r
0
. The horizontal axis has a unit of r
2
c
=D,
which characterizes the timescale of the kinetics of geminate recombination in a particular
system For example, in nonpolar liquids at room temperature r
2
c
=D
f
10
8
sec. Unfortu-
nately, the analytical treatment presented by Hong and Noolandi [13] is rather compli-
cated and inconvenient for practical use. Tabulated values of W(t) can be found in Ref. 14.
The pair survival probability of geminate ion pairs can also be calculated numerically [15].
In some cases, numerical methods may be a more convenient approach to calculate W(t),
especially when the reaction cannot be assumed as totally diusion-controlled.
It can be shown that for the totally absorbing boundary condition, and for R<<r
c
,
the long-time behavior of the pair survival probability W(t) is described by
Wt exp
r
c
r
0
_ _
1
r
c
pDt
p
_ _
25
Figure 1 Electron escape probability as a function of the applied electric eld. The solid lines
are obtained from Eq. (23) for dierent values of the initial electron cation distance r
0
. The broken
lines are calculated for r
0
= 1 nm from the numerical solution of Eq. (16) with the sink term given by
k
r
(r) = A exp[a(rd)], where a = 10 nm
1
and d = 0.6 nm. Dierent lines correspond to dierent
values of A from 10
13
(the lowest broken curve) to 10
8
, in decadic intervals. The parameter values
were assumed as e = 4, T = 298 K, and D = 510
3
cm
2
/sec.
This asymptotic form of W(t) is also plotted in Fig. 2 (as dashed lines). However, we see
that this approximation is valid only when the pair survival probability slightly exceeds the
escape probability, so its practical importance is rather limited.
When a strong electron acceptor (electron scavenger) is added in the irradiated
system, some of the electrons will react with the scavenger before they recombine with
their parent cations. Therefore the measurement of the yield of the scavenging products as
a function of the scavenger concentration can be used to monitor the geminate recombi-
nation, and the electron scavenging technique has proved to be an important tool in ex-
perimental studies.
The geminate recombination in the presence of a scavenger can be described by the
Smoluchowski equation [Eq. (2)] with an additional term representing the loss of the
geminate pairs by scavenging reactions
Bw
s
Bt
D j
2
w
s
1
k
B
T
jw
s
jV
_ _
k
s
C
s
w
s
r; t; C
s
26
Here k
s
denotes the rate constant for the scavenging reaction and C
s
is the scavenger
concentration. The probability density for the geminate pairs, w
s
(r,t,C
s
), may be related to
the corresponding probability density in the absence of scavenger, w(r,t), through
w
s
r; t; C
s
wr; texpk
s
C
s
t 27
Figure 2 Survival probability of geminate ion pairs as a function of time. The two solid lines
correspond to two dierent values of the initial electroncation distance. The broken lines show the
asymptotic kinetics calculated from Eq. (25). The value of the escape probability for r
0
= 0.5r
c
is
indicated by u. (From Ref. 13.)
which is easily veried by substitution. Experimentally important is the total scavenging
probability u
s
(k
s
C
s
), which is dened as the probability that an electron reacts with a
scavenger before recombination with a positive ion. By making use of Eq. (27), u
s
(k
s
C
s
)
was shown to satisfy the relation
u
s
k
s
C
s
k
s
C
s
_
l
0
Wtexpk
s
C
s
tdt k
s
C
s
Wk
s
C
s
28
where Ws stands for the Laplace transform of W(t). This equation shows that the total
scavenging probability is proportional to the Laplace transform, Wk
s
C
s
, of the pair
survival probability in the absence of scavenger W(t) [16]. Eq. (28) has a great practical
importance, as it allows us to calculate the lifetime distribution of the geminate pairs from
measurements of the yield of the scavenging products by inverse Laplace transformation.
This equation may also be considered as a generalization [17] of the SternVolmer relation
widely used in photochemistry to the case where the survival probability W(t) is not de-
scribed by an exponential function.
The theory of geminate recombination presented so far is based on the solutions of the
Smoluchowski equation for an isolated pair of a cation and an electron, which are assumed
to perform a diusive motion in each others Coulomb eld. The single-pair approach has
proved to be very useful in modeling early stages of the electronion recombination
processes in various systems, and was applied to interpret numerous experimental results.
There are physical situations, especially in photochemical studies, where ionization is weak
and the geminate electronion pairs are separated from one another by distances much
larger than the Onsager radius. In such systems, the single-pair model of geminate re-
combination is directly applicable. On the other hand, ionization events in radiation tracks
are known to form specic spatial patterns, in which only a fraction of the produced
electroncation pairs may be treated as independent of one another. The single-pair model is
then only an approximation, and the multipair eects due to the interactions between the
neighboring pairs of charges have to be taken into account.
Analytical treatment of the diusion-reaction problem in a many-body system
composed of Coulombically interacting particles poses a very complex problem. Except
for some approximate treatments, most theoretical treatments of the multipair eects
have been performed by computer simulations. In the most direct approach, random
trajectories and reactions of several ion pairs were followed by a Monte Carlo simulation
[18]. In another approach [19], the approximate Independent Reaction Times (IRT)
technique was used, in which an actual reaction time in a cluster of ions was assumed to
be the smallest one selected from the set of reaction times associated with each independent
ion pair.
An important result of the theoretical studies of the multipair eects is that the
recombination kinetics in a cluster of ions, in which the initial separation between
neighboring cations is
f
1 nm, is faster than the corresponding decay kinetics of a single
ion pair [18]. Furthermore, the escape probability is lower than the Onsager value [Eq.
(15)], and decreases with increasing number of ion pairs in the cluster (a relative decrease
of about 30% for two ion pairs, and about 50% for ve ion pairs). The average electron
escape probability in radiation tracks obviously depends on the distribution of ionization
events in the tracks, which is determined by the type of radiations and their energy.
Calculations of the external electric eld eect on the escape probability in multipair
clusters [18] have shown that signicant deviations from the results of the single-pair
theory are expected at high electric elds. At low elds, the escape probability is a linear
function of the eld, and the slope-to-intercept ratio of this dependence is almost the same
as that obtained in the single-pair theory [20] [cf. Eq. (24)].
A study of electron scavenging in multipair clusters [21] has shown that the total
scavenging probability decreases with increasing number of ion pairs in the cluster.
However, the Laplace transform relationship [Eq. (28)] between the scavenging probabil-
ity and the recombination kinetics was found to work reasonably well also in the multipair
case.
In this section, a theory of geminate recombination of charged species is presented by
fully taking into account the Coulomb interaction between the species. While for nonpolar
systems, the theory of geminate ion recombination in its full form has to be used, some
simple approximate theories can be used for systems of high polarity. An important ex-
ample is water, where the Onsager radius is only 0.7 nm, and is shorter than typical elec-
tron thermalization distances of a few nanometers. In this case, the Coulomb interaction
between the ionization products is not so important and, in the rst approximation, it may
even be neglected, as it was performed in numerous theoretical studies. The advantage of
this approach is that the analytical expression describing the geminate recombination of
uncharged species are much simpler than those for the geminate ion recombination.
However, theoretical modeling of the geminate recombination processes in water is still
complicated, even if one neglects the Coulomb interactions. This is because the primary
ionization products in water undergo a series of chemical reactions, which proceed on the
timescale shorter than that of the charge recombination.
Geminate Ion Recombination in High-Mobility Systems
The theory of geminate recombination presented in Sec. 10.1.2 (Diusion-Controlled
Geminate Ion Recombination) is based on the assumption that the relative motion of
electrons and cations that constitute geminate pairs is described by the diusion equation.
In a real system, the motion of a particle may be treated as ideal diusion when its scat-
tering by atoms or molecules of the system is very frequent, and its mean free path, k, is
much shorter compared with the typical length involved in the problem. In the case of the
ion recombination, it is reasonable to take as the typical length involved in the problem
the range of the Coulomb interactions in the considered system, so the applicability of the
diusion theory of geminate recombination is theoretically limited to systems where the
scattering mean free path is much shorter than the Onsager radius (k<<r
c
). In a simple
model, the mean free path of charged particles is proportional to their mobility l. There-
fore the diusion theory of geminate recombination will not be applicable, when the
mobility of charges is too high. In fact, deviations from the diusion theory were ex-
perimentally observed in systems where the electron mobility exceeds
f
100 cm V
1
sec
1
.
Limitations of the diusion approach also become apparent from the considerations
based on energy. In the conventional diusion approach, it is assumed that particles are
always in thermal equilibrium with the system, and that their velocity distribution is close
to the MaxwellBoltzmann distribution. When the mean free path is long, and the scat-
tering events not so frequent, electrons are no longer able to eectively dissipate the kinetic
energy they acquire in the Coulomb eld of the cations. The average electron energy is
then signicantly higher than the thermal level.
In this physical picture of geminate recombination in high-mobility systems, it is no
longer valid to use the space criterion of reaction expressed in terms of the distance.
Instead, the energy criterion of reaction expressed in terms of energy or, more preferably,
the energy-dependent reaction cross section should be used.
Because of the inecient dissipation of their kinetic energy, electrons in high-mobility
systems are more likely to escape geminate recombination than predicted by the diusion
theory. Such an eect has been conrmed by the results of a computer simulation study [22]
presented in Fig. 3. In this study, classical electron trajectories in the Coulomb eld of a
cation were calculated, starting at a distance r
0
from the cation, and the electron scattering
was modeled in such a way that the electron velocity was randomized at each collision to
restore the MaxwellBoltzmann distribution. The times between the collisions were selected
from an exponential distribution, and its mean value, s, was used to characterize the
strength of the dynamic interaction between the electron and the solvent. The mean free
time s may be related to the mean free path by k/r
cc
1.6s. For each electron, the simulation
was carried out until either the reaction occurred, or the electron was separated from the
cation to a distance much larger than r
c
. An energy criterion of reaction was used, namely,
the electron was assumed to have reacted once its total energy in the Coulomb eld of the
cation was reduced below 10k
B
T.
According to Fig. 3, the Onsager result [Eq. (15)], which shows the escape prob-
ability in the diusion-controlled geminate recombination, gives the lower bound for the
simulation results. The simulation results obtained for the lowest value of s (s = 0.05) are
Figure 3 Escape probability as a function of the initial electroncation distance. The lower broken
curve is calculated from the Onsager equation [Eq. (15)]. The numerical results for dierent mean
free times s were taken from Ref. [22]. The unit of s is r
c
/(k
B
T/m)
0.5
, where m is the electron mass.
The upper broken curve was calculated using the energy diusion model. (From Ref. 23.)
very close to the Onsager result. At higher values of the mean free time, the escape
probability exceeds the Onsager result and signicantly increases with increasing s.
The upper bound of the escape probability, corresponding to s!l, can also be
analytically calculated. In this limit, the electron is allowed to make many revolutions in
the same orbit around the cation before it is scattered into another orbit. Under this
condition, the electron motion may be described as diusion in energy space [23]. The
escape probability calculated by using the energy diusion model is also included in Fig. 3.
We see that the simulation results for nite s properly approach the energy diusion limit.
Computer simulation has also been used to calculate the external electric eld eect
on the geminate recombination in high-mobility systems [22]. For the mean free time s
exceeding
f
0.05, the eld dependence of the escape probability was found to signicantly
deviate from that obtained from the diusion theory. Furthermore, the slope-to-intercept
ratio of the eld dependence of the escape probability was found to decrease with
increasing s. Unlike in the diusion-controlled geminate recombination, this ratio is no
longer independent of the initial electron-ion separation [cf. Eq. (24)].
The model of electron scattering in high-mobility systems applied in the simulations
is rather simplied. Especially, the assumption that the electron velocity is randomized at
each scattering to restore the MaxwellBoltzmann distribution may be an oversimplica-
tion. If the dissipation of energy by electron collisions in a real system is less ecient than
that assumed in the simulation, the escape probability is expected to further increase.
The electronion recombination in high-mobility systems has also been analyzed in
terms of the fractal theory [24,25]. It was postulated that even when the fractal dimension
of particle trajectories is not equal to 2, the motion of particles is still described by
diusion but with a distance-dependent eective diusion coecient DV(r) =D(1+l/
r)
1
, where the parameter l is proportional to the mean free path k [24]. However, when
the fractal dimension of trajectories is not equal to 2, the motion of particles is not
described by orthodox diusion.
1.3. Bulk Ion Recombination
Diusion-Controlled Bulk Ion Recombination
When the motion of electrons and positive ions in a particular system may be described as
ideal diusion, the process of bulk recombination of these particles is described by the
diusion equation. The mathematical formalism of the bulk recombination theory is very
similar to that used in the theory of geminate electronion recombination, which was de-
scribed in Sec. 10.1.2 (Diusion-Controlled Geminate Ion Recombination). Geminate
recombination is described by the Smoluchowski equation for the probability density w(r,t)
[cf. Eq. (2)], while the bulk recombination is described by the diusion equation for the space
and time-dependent concentration of electrons around a cation (or vice versa), c(r,t),
Bcr; t
Bs
D j
2
cr; t
1
k
B
T
jcr; tjVr
_ _
29
The two equations have the same mathematical form, although they deal with dierent
physical quantities. The initial and boundary conditions are also somewhat dierent. In the
bulk recombination, the initial electron concentration is assumed to be uniformin the space
and equal to the average concentration c
0
cr; 0 c
0
30
The boundary condition at innite separation is given by
lim
r!l
cr; t c
0
31
where we assume that the average electron concentration changes little during the reaction.
The methods used in geminate recombination to account for the reaction are also
applicable to bulk ion recombination. In the simplest case of fully diusion-controlled
recombination, the reaction can be represented by the totally absorbing boundary con-
dition
cR; t 0 32
where R is the reaction distance. For partially diusion-controlled recombination, we may
use the boundary condition in the form
D
Bcr; t
Br

cr; t
k
B
T
BVr
Br
_ _
rR
pcR; t 33
where the left-hand side represents the ux through the reaction surface, and the reactivity
parameter p is a measure of the intrinsic rate constant at the reaction distance.
An example of numerical solutions of Eq. (29) for the attractive Coulomb potential,
subject to the initial and the boundary conditions (30)(32), is presented in Fig. 4 [26]. The
gure shows how the initially uniform electron concentration gradually decreases in the
vicinity of the cation until the steady state is established. The rate of reaction is determined
by the diusive ow of electrons from large distances toward the reaction sphere.
Figure 4 Time evolution of the normalized concentration of electrons around the cation c(r,t)/c
0
for D=10
4
cm
2
/sec and r
c
= 0.7 nm. Dierent curves correspond to dierent times from 10
14
to
10
7
sec, in decadic intervals. (From Ref. 26.)
The time-dependent rate coecient for the bulk ion recombination may be obtained
as the total current of particles owing through the reaction surface at r = R, divided
by c
0
,
kt 4pR
2
D
Bcr; t
Br

cr; t
k
B
T
BVr
Br
_ _
rR
_
c
0
34
The long-time limit of k(t) denes the steady state rate constant of the bulk ion recom-
bination, which for the totally diusion-controlled recombination is calculated as [27]
k
4pDr
c
1 exp
r
c
R
_ _ 35
When the reaction distance is short in comparison with the range of the Coulomb inter-
action (R<<r
c
), Eq. (35) reduces to the so-called DebyeSmoluchowski expression
k
D
4pDr
c
36a
This expression is a fundamental result of the theory of bulk ion recombination and has
been extensively used in interpreting experimental results of diusion controlled reactions.
The DebyeSmoluchowski expression can also be written in terms of the mobility,
k
D

4pe
e
l 36b
where we have used the Einstein relation between the diusion coecient and the mobility
l/D=e/k
B
T.
In the case of partially diusion-controlled recombination, which is described by Eq.
(33), the recombination rate constant is calculated as [28]
k
4pDr
c
1 1
Dr
c
pR
2
_ _
exp
r
c
R
_ _
37
The rate constants given by Eqs. (35)Eqs. (37) give the steady state rate constants of bulk
ion recombination. As seen from Fig. 4, it takes some time before the steady state is
established, and, in general, the rate coecient of the bulk ion recombination is time-
dependent. Although no simple analytical expression is available, which describes k(t) in
the whole time domain, the expression for the asymptotic behavior of k(t) at long times is
easily obtained. For fully diusion-controlled recombination, we have
kt !l
4pDr
c
1 expr
c
=R
1
expr
c
=R
1 expr
c
=R
r
c
pDt
p
_ _
38
It was shown [26] that in water (r
c
=0.7 nm), the transient eect in the bulk ion recom-
bination may be signicant on the timescale shorter than a nanosecond. For nonpolar
systems (r
c
f
30 nm), the transient eect in Eq. (38) is much smaller, and the time de-
pendence of the rate coecient is not likely to be experimentally observed.
Bulk recombination is a many-body problem. It is not so obvious whether the ap-
proach based on Eqs. (2934) correctly describes the many-body character of bulk recom-
bination. Tachiya [29] formulated the rate of bulk recombination in terms of the pair
survival probability of geminate recombination and showed that the approach described
above is exact only when the minority reactants are xed and the majority reactants are
mobile (target problem). The above approach is not exact when the majority reactants are
xed and the minority reactants are mobile (trapping problem), or when the concen-
trations of two reactants are comparable, although it gives a very good approximation in
most cases of interest.
Because of its importance for experimental studies, we will also discuss the eect of
an applied electric eld on the rate constant of bulk ion recombination. Within the frame-
work of the diusion theory, this eect can be calculated by solving the diusion equation
[Eq. (29)] with the potential energy given by Eq. (21) under relevant initial and boundary
conditions. Analytical solutions of this problem, both for the totally absorbing [Eq. (32)]
and the partially reecting [Eq. (33)] boundary conditions, are found in Ref. 30. In the case
of totally diusion-controlled recombination, the rate constant is found to increase with
increasing eld strength. The general expression for the electric eld dependence of the
recombination rate constant, k( F), obtained in Ref. 30 is quite complicated and involves
an innite series summation. An expansion of this expression in the Taylor series up to the
rst order in F gives [30]
kF
4pDr
c
1 expr
c
=R
1
expr
c
=R
1 expr
c
=R
eFr
c
2k
B
T
_ _
39
The increase of k with increasing eld strength is explained by an enhanced rate of en-
counter between positively and negatively charged particles because of their drift in the
opposite directions in the presence of an external eld. However, in nonpolar systems, this
eect is very weak and the recombination rate constant is almost independent of the elec-
tric eld.
The results obtained in Ref. 30 for partially diusion-controlled recombination show
that the eld dependence of the recombination rate constant is aected by both the
reaction radius R and the reactivity parameter p [cf. Eq. (33)]. Depending on their relative
values, the rate constant can be increased or decreased by the electric eld. The latter eect
predominates at low values of p, where the reactants staying at the encounter distance are
forced to separate by the electric eld.
Because of space limitation, we have discussed only a part of aspects of the theory of
diusion-controlled ionic processes, which we believe to be essential for understanding the
bulk phase of ion recombination in irradiated systems. Discussions of other aspects of
diusion-controlled ionic processes are found in monographs on the diusion-controlled
reactions [31]. One important aspect that was only briey touched in this section concerns
the theoretical models to account for the reaction between ions (the nal step of recombi-
nation). We have discussed the models, which introduce specic boundary conditions at the
reaction distance [Eqs. (32) and (33)] to account for the reaction. In a more general
approach, the reaction may be accounted for by introducing a sink term, as it was considered
in geminate recombination [cf. Eqs. (16) and (17) in Sec. 10.1.2 (Diusion-Controlled
Geminate Ion Recombination)]. Such an approach allows us to treat the case where the
reaction occurs not only at the contact distance, but over a range of distances, as in the case
of electron transfer reactions. Another important aspect concerns the inuence of the
solvent structure on the diusive transport of ions. This is exhibited as the potential of mean
force and hydrodynamic eects. However, these eects are usually overwhelmed by the
Coulomb attraction between the ions, and may be safely neglected, especially in nonpolar
systems. The competition eects in the diusion-controlled bulk ion recombination are also
expected to inuence the recombination rate constant at high ion concentrations, although
they may not be very important in normal experimental conditions [32].
The theory of diusion-controlled recombination presented in Secs. 10.1.2 (Dif-
fusion-Controlled Geminate Ion Recombination) and 10.1.3 (Diusion-Controlled
Bulk Ion Recombination) may not be applicable to a class of disordered solid state
systems, including amorphous semiconductors and organic glasses, where the charge
transport is strongly inuenced by the processes of trapping and detrapping of charge
carriers. The transport of charged particles in such systems is usually described as the
continuous time random walk [33,34] or using the fractional diusion approach [35].
These two approaches have also been used in the theoretical studies of both geminate and
bulk ion recombination in the disordered systems [36,37]. However, in those studies, the
Coulomb interaction between the charged particles was not taken into account.
Bulk Ion Recombination in High-Mobility Systems
The diusion theory of bulk electronion recombination presented in Sec. 10.1.3 (Dif-
fusion-Controlled Bulk Ion Recombination) is not applicable to systems where the elec-
tron mobility is high. If the mobility exceeds
f
100 cm
2
V
1
sec
1
, eects due to the nite
mean free path for electron scattering become signicant, and the electron motion can no
longer be described as ideal diusion. The general physical picture of electron transport
processes and reactions in high-mobility systems is essentially the same both in the
geminate and the bulk phases of recombination, and has already been discussed in Sec.
10.1.2 (Geminate Ion Recombination in High-Mobility Systems). In short, when the
electron mean free path increases, the character of its motion gradually changes from
diusive to ballistic. In place of the spatial diusion of electrons and cations toward one
another, the rate-determining process for their recombination becomes the dissipation of
the kinetic energy the particles acquire in the mutual Coulomb eld. In consequence, the
electronion recombination rate constants in high-mobility systems are expected to be
signicantly lower than the DebyeSmoluchowski value k
D
predicted by the diusion
theory [cf. Eq. (36)]. This was conrmed by the experimental results, which will be dis-
cussed later in this chapter.
An estimate of the electronion recombination rate constant in high-mobility systems
based on an empirical model of energy dissipation processes was provided by Warman [38].
He related the rate constant to the eld dependence of the electron mobility, and proposed
an empirical formula
k
k
D
1
55T
4
e
2
F
2
10
_ _
1
40
Here F
10
denotes the critical electric eld strength expressed in units of V/m, at which the
electron mobility deviates 10% from the thermal mobility, and is used as a measure of the
rate of the electron energy dissipation in a particular system. Despite its simplicity, Eq. (40)
is shown to give reasonable estimates of the electronion recombination rate constant for
some of the experimentally studied high-mobility systems.
The breakdown of the diusion theory of bulk ion recombination in high-mobility
systems has been clearly demonstrated by the results of the computer simulations by
Tachiya [39]. In his method, it was assumed that the electron motion may be described by
the Smoluchowski equation only at distances from the cation, which are much larger than
the electron mean free path. At shorter distances, individual trajectories of electrons were
simulated, and the probability that an electron recombines with the positive ion before
separating again to a large distance from the cation was determined. The value of the re-
combination rate constant was calculated by matching the net inward current of electrons
obtained from the simulation results with that derived from the Smoluchowski equation at
large distances. To simulate electron trajectories, he used a simplied model of electron
scattering, in which the electron velocity was randomized at each collision to restore the
MaxwellBoltzmann distribution. An energy criterion of recombination was used, namely,
an electron was assumed to have reacted once its total energy in the Coulomb eld of the
cation was reduced below a certain critical energy.
The simulation results of the electronion recombination rate constant obtained in
Ref. 39 are plotted in Fig. 5. The gure shows that the rate constant becomes lower than the
DebyeSmoluchowski value k
D
when the electron mean free path exceeds
f
0.01r
c
. At
higher values of k, the ratio k/k
D
further decreases with increasing mean free path. The
simulation results are found to be in good agreement with the experimental data on the
electronion recombination rate constant in liquid methane, which are also plotted in Fig. 5.
The dependence of the electronion recombination rate constant on the mean free
path for electron scattering has also been analyzed on the basis of the FokkerPlanck
equation [40] and in terms of the fractal theory [24,25,41]. In the fractal approach, it was
postulated that even when the fractal dimension of particle trajectories is not equal to 2,
the motion of particles is still described by diusion but with a distance-dependent
eective diusion coecient. However, when the fractal dimension of trajectories is
not equal to 2, the motion of particles is not described by orthodox diusion. For the
Figure 5 The rate constant of bulk electronion recombination, relative to the Debye
Smoluchowski value [Eq. (36)], as a function of the electron mean free path k. The solid line
represents the simulation results, and the circles show the experimental data for liquid methane [49].
(From Ref. 39.)
relation between the fractal dimensions of reactant trajectories and the transport-limited
reaction rate, see Ref. 42.
In the limit of an innitely long mean free path, the bulk electronion recombination
may be described using the energy diusion model [43,44]. This model is especially
relevant to the electronion recombination processes in the gas phase.
The theoretical models of the bulk electronion recombination presented so far in
this section use only one parameter, namely the electron mean free path, to characterize
the electron transport processes in a wide class of high-mobility systems. This is
undoubtedly an oversimplication, and more realistic models of electron scattering have
to be used, if one wants to achieve a better understanding of the bulk recombination
processes in a given system. Such models, which use electron scattering cross sections, were
applied in the simulations of the electronion recombination in liquid methane [45] and
liquid argon [46]. In the case of methane, the mean free path for elastic electron scattering
was determined from the experimental electron mobility, and the inelastic scattering was
simulated using model cross sections for vibrational and electronic excitations. In the
simulation for argon [46], the electron motion was described using a model, which takes
account of dierent rates of energy and momentum transfers in electron collisions, in
accordance with the CohenLekner theory [47] of hot electrons in liquids. In both
Figure 6 Dependence of the electronion recombination rate constant on the external electric eld
F, calculated for dierent values of the electron mean free time s. The unit of F is e=er
2
c
, and that of s
is r
c
/(k
B
T/m)
0.5
. The simulation results of Morgan [45] for liquid methane at 120 K are shown by
crosses. (From Ref. 48.)
simulations, a reasonable agreement of the calculated rate constants with the experimental
results has been obtained.
Experimental data on the electronion recombination in high-mobility systems are
usually obtained by measuring the transient conductivity of an ionized system in the
presence of an external electric eld. The applied eld increases the average kinetic energy
of charge carriers. As the dissipation of energy is believed to be the rate-determining
process for the electronion recombination in high-mobility systems, the recombination
rate constant in these systems should decrease with increasing eld strength. Such an
expectation has been conrmed by the simulations [48] in which the eld dependence of the
rate constant was calculated for systems characterized by dierent values of the electron
mean free time H (the mean free time may be related to the mean free path by k/r
cc
1.6s).
The results are presented in Fig. 6. We see that as the mean free time increases, the sup-
pression of the electronion recombination by the electric eld becomes stronger. In the
model of the electron scattering assumed in Ref. 48, the electron velocity was randomized
at each collision to restore the MaxwellBoltzmann distribution. However, in real systems,
the electron energy dissipation by collisions is usually not so ecient, and the decrease of
the recombination rate constant with increasing electric eld should be even stronger than
calculated in Ref. 48. This expectation is supported by the simulation results for liquid
methane [45], also included in Fig. 6, which were obtained by using a realistic model of
electron scattering in that system.
2. PICOSECOND AND SUBPICOSECOND PULSE-RADIOLYSIS STUDIES
OF GEMINATE ION RECOMBINATION IN LIQUID HYDROCARBONS
2.1. Introduction
The geminate ion recombination in liquid hydrocarbons has been studied both by station-
ary experiments and by kinetics data. Although the kinetics data of pulse radiolysis exper-
iments give more detailed information about the geminate recombination than stationary
data such as scavenger experiments, the very high time-resolved spectroscopy is indis-
pensable for studies on the kinetics of the geminate ion recombination. The experimental
studies on the kinetics of the geminate ion recombination have advanced with the devel-
opment of picosecond and subpicosecond pulse radiolysis development.
Here the progress in the picosecond and subpicosecond pulse radiolysis is described
rst and then the experimental studies on the kinetics of the geminate ion recombination is
explained in connection with their application to advanced technology such as the next
generation nanolithography and nanotechnology.
2.2. Progress in Picosecond and Subpicosecosecond Pulse Radiolysis
History of Picosecond and Subpicosecosecond Pulse Radiolysis
With the development of the picosecond pulse radiolysis, the kinetics data of the geminate
ion recombination have been directly obtained. The history of picosecond and subpico-
second pulse radiolysis is shown in Fig. 7. Very recently, the rst construction of the
femtosecond pulse radiolysis and the improvement of the subpicosecond pulse radiolysis
started in Osaka University.
The rst picosecond pulse radiolysis experiment was carried out in the late 1960s by
the so-called stroboscopic method (generally pomp and probe method) at University of
Toronto [50]. Picosecond electron pulse trains generated with a S-band linear accelerator
(linac) as an irradiation source and the Cerenkov light induced from the electron pulse
trains as an analyzing light were used. The system was very sophisticated, but S/N ratio
is not high. Therefore the operation of the system for obtaining small absorption and
the detailed kinetics data is very dicult. Similar system was developed in Hokkaido
University more than 10 years later [51]. The combination of picosecond electron pulse
trains with high time-resolved detection systems was applied to the picosecond pulse
radiolysis with optical [52] and conductivity [53] spectroscopy. Measurable time domain of
these picosecond pulse radiolysis systems using picosecond electron pulse trains were
limited from the time resolution of the system to 350 and 770 psec determined by the pulse
interval in the pulse trains of S-band and L-band linacs, respectively. The overlapping of
the correct signal with the signal of slow decaying intermediates species produced by the
preceding picosecond electron pulses made dicult the detailed analysis of the kinetics of
intermediates. These systems were unable to study the geminate ion recombination in
irradiated liquid hydrocarbons.
The stroboscopic pulse radiolysis with the single bunch electron pulse instead of
pulse trains started in Argonne National Laboratory in 1975 [54]. The research elds have
been extended by the stroboscopic pulse radiolysis with the picosecond single electron
bunch, although most of researches had been limited to hydrated and solvated electrons in
the aqueous and alcoholic solutions. This system was unable to study the kinetics of the
geminate ion recombination in liquid hydrocarbons until the modication of the Argonne
linac in 1983, which made possible the quality measurements of the weak absorption.
Figure 7 History of picosecond and subpicosecond pulse radiolysis and the start of construction of
the rst femtosecond pulse radiolysis.
The combination of the picosecond single electron bunch with streak cameras, in-
dependently developed in 1979 at Argonne National Laboratory [55] and at University of
Tokyo by us [56], enabled the very high time resolution for emission spectroscopy. The
research elds have been extended to organic materials such as liquid scintillators [5557],
polymer systems [58], and pure organic solvents [59]. The kinetics of the geminate ion
recombination were studied [55,57,59].
The picosecond pulse radiolysis system in the combination of very fast response pho-
todiode with the transient digitizer (the time resolution of about 800 psec) was developed
by us in 1982 [60]. This system was the rst picosecond pulse radiolysis system that could
measure the kinetics of ions and triplet states on subnanosecond timescale by using only
one picosecond single bunch electron pulse. This system has no limitation of nano- and
microsecond timescale measurement and the radiation damage of the samples of the ex-
periments performed by this system was so much less than preceding picosecond pulse
radiolysis. Most experiments of geminate recombination of solute ions were performed by
this system [6066]. The response time of this system using the sampling oscilloscope
instead of the transient digitizer was 200 psec [61], but the radiation damage of the samples
was very large.
The important picosecond pulse radiolysis study on geminate recombination of solute
ions in liquid alkanes [65] was carried out in the combination of the picosecond pulse
radiolysis system composed of very fast response photodiode and the transient digitizer [60]
with the specially designed picosecond pulse radiolysis system [67] composed of a streak
camera (the time resolution of 50 psec) developed in 1984. Our experiment [65] showed for
the rst time that the geminate recombination of solute ions could be analytically explained
by the extended Smoluchowski equation [13,68]. The S/N ratio was not high because of a
limited dynamic range of the streak camera at that time, but the radiation damage of the
samples was very low. The proof of the principle of the twin linac system, where one linac
produced picosecond electron pulses as radiation source and the other linac produces the
Cherenkov light as monitor light, was reported in 1985 [69] and the construction of the
system was carried out in 1987 [70]. Although the twin linac system was very interesting
system, the operation of the system was very dicult and it takes too much eort to obtain
the data of radiation chemistry. The radiation damage of the samples was also very large.
After the LL (LaserLinac) twin picosecond pulse radiolysis was developed in 1991 [71], the
twin linac system was not used any more. Very important results for radiation chemistry
used by the twin linac system were the measurement of very rapid formation of alkyl
radicals in irradiated liquid alkanes within the time resolution of the system and it indicates
the importance of the excited radical cations in radiolysis of cyclohexane [66].
The LL twin picosecond pulse radiolysis system, which used picosecond semiconduc-
tor laser as monitor light instead of Cherenkov light of the twin linac pulse radiolysis, was
successfully developed by us for the rst time in 1991 [71]. It is the rst picosecond pulse
radiolysis in the combination of the single electron bunch with laser monitor light, although
several trials of the picosecond pulse radiolysis with the single electron bunch and laser
monitor light had attempted, but the system was not correctly operated [72]. Because the
operation of the LL twin picosecond pulse system was much easier than that of the twin
linac, pulse radiolysis and the laser diode as monitor light enabled the absorption spectro-
scopy from visible to infrared region in picosecond time range for the rst time [71]. The
kinetics of the geminate recombination of both electrons and cation radicals were rst
measured on a picosecond timescale in the same sample and agree with each other on
picosecond timescale from 50 psec after a pulse [71]. However, it was very dicult to obtain
the complete transient absorption spectra by this system because the laser diodes are not
tunable light source.
We solved the lack of the tunability of the LLtwin pulse radiolysis by the development
of the laser synchronized picosecond pulse radiolysis in 1995 at Osaka University [73]. The
time resolution of pulse radiolysis had remained about 30 psec for 30 years since the late
1960s (Fig. 7), although many modications had been performed for picosecond pulse
radiolysis techniques. The femtosecond monitoring laser pulse is synchronized with both the
electron pulses from the electron gun and accelerating electron pulses through the accel-
erating tubes in the laser synchronized picosecond pulse radiolysis system, although the
picosecond laser pulse is synchronized with only the electron pulse from the electron gun in
the LL twin linac system. Although the time resolution of the laser synchronized pulse
radiolysis at that time was 30 psec, this system had the possibility of the development of the
femtosecond pulse radiolysis.
The time resolution of 2 psec [74] for 2-mm optical path sample cell was obtained as
shown in Fig. 8 by using laser synchronized subpicosecond pulse radiolysis with the
femtosecond single electron bunch [76] and a jitter compensation system with 200-fsec
streak camera [74]. In this case, the time dierence between electron beam and light passing
through a sample is 1.8 psec. Therefore the time resolution is mainly determined by the
optical path length. The time resolution of 800 fsec [75] for 0.5-mm optical path sample cell
was obtained as shown in Fig. 9, but the S/N ratio is very low. The S/N ratio of the laser
synchronized subpicosecond pulse radiolysis was greatly improved by the double-pulse
method as shown in Fig. 10 [77]. Now the kinetics of the geminate ion recombination of
Figure 8 The time-dependent behavior of the hydrated electron obtained in the subpicosecond
pulse radiolysis of neat water using 2-mm optical path sample cell, monitored at the wavelength of
780 nm.
electron and radical cations has been directly studied by the laser synchronized subpico-
second pulse radiolysis with the double-pulse method. The details of the double-pulse
method are described in the next section.
Now several picosecond pulse radiolysis systems are operating in Argonne National
Laboratory, Brookhaven National Laboratory and University of Tokyo and are under
construction in University of Paris South and Waseda University, although only one sub-
picopulse radiolysis is operating in Osaka University.
Figure 9 The time-dependent behavior of the hydrated electron obtained in the subpicosecond pulse
radiolysis of neat water using 0.5-mmoptical path sample cell, monitored at the wavelength of 780 nm.
Figure 10 The geminate decay of the radical cation in irradiated neat n-dodecane observed by the
subpicosecond pulse radiolysis before (a) and after (b) the improvement of the system by mainly
using the double-pulse method.
Subpicosecond Pulse Radiolysis [74,77]
The subpicosecond pulse radiolysis [74,77] detects the optical absorption of short-lived
intermediates in the time region of subpicoseconds by using a so-called stroboscopic tech-
nique as described in Sec. 10.2.2 (History of Picosecond and Subpicosecosecond Pulse
Radiolysis). The short-lived intermediates produced in a sample by an electron pulse are
detected by measuring the optical absorption using a very short probe light (a femtosecond
laser in our system). The time prole of the optical absorption can be obtained by chang-
ing the delay between the electron pulse and the probe light.
Stroboscopic pulse radiolysis can achieve high time resolution because the time res-
olution of the stroboscopic pulse radiolysis does not depend on the time resolution of the
detection systems such as photodiodes and oscilloscopes. The time resolution is principally
determined by the lengths of the electron pulse and probe light and the timing accuracy (or
jitter) between them as shown in Fig. 11. Assuming that the envelopes of both the electron
pulse and probe light and the timing uctuation have a Gaussian distribution, the response
function, g
1
(t), can be expressed as follows,
g
1
t
1
2pr
p e
t
2
2r
2
41
r
2
r
2
i
r
2
b
r
2
j
42
where r
b
is the length of the electron pulse (rms), r
i
is the length of the probe light (rms)
and r
j
is the timing uctuation (rms).
However, the time resolution is also degraded by the velocity dierence between the
light and the electron pulse in a sample. The time in which the electron pulse passes
through a sample is given by L/(bc), where L is the optical length of the sample, c is
the velocity of light in vacuum, and b is the ratio of the velocity of the electron to c. On the
other hand, in the case of light, the time in which it passes is given by Ln/c, where n is the
refractive index of the sample. Therefore the time resolution is degraded with increasing
Figure 11 The components of the timing jitter of the laser synchronized subpicosecond pulse
radiolysis. r
b
is the length of the electron pulse (rms), r
i
is the length of the probe light (rms), and r
j
is the timing uctuation (rms).
thickness of the sample. The response function with the eect of velocity dierence, g
2
(t),
can be deduced from the denition of the response function as follows,
g
2
t
c
p
p
L n
1
b
_ _
_
2ct L n
1
b
_ _
2
2rc
p
2ct L n
1
b
_ _
2
2rc
p
e
x
2
dx 43
When the optical length of the sample is much shorter than the other factors such as the
length of the electron pulse, the response function takes on a Gaussian shape. As the
optical length increases, the shape of the response function becomes trapezoidal. Fur-
thermore, a thick sample causes the prolongation of the electron pulse by electron
scattering, which leads to the degradation of time resolution. Therefore the experiment
to observe ultrafast phenomena requires the use of a thin sample.
Fig. 12 shows the subpicosecond pulse radiolysis system. The system consists of a
subpicosecond electron linac as an irradiation source, a femtosecond laser as an analyzing
light, and a jitter compensation system. A sample was irradiated by a subpicosecond
electron single pulse. The subpicosecond electron single pulse was obtained by compressing
a 30-psec electron single pulse from the ISIR L-band linac with a magnetic pulse
compressor. This system can compress the width of electron pulse to approximately 125
fsec (FWHM) [76]. The time-resolved optical absorption was detected with a femtosecond
laser. A mode locked ultrafast Ti:Sapphire laser (Tsunami, Spectra-Physics Lasers, Inc.)
was synchronized to the ISIR L-band Linac using a commercially available phase lock
loop. The width of the laser pulse was 60 fsec (FWHM). The intensity of the laser pulse was
measured by a Si photodiode. The timing between the electron pulse and the laser pulse was
controlled by radio frequency (RF) system. The time prole of the optical absorption could
be obtained by changing the phase of the RF with an electrical phase shifter.
The jitter between the laser pulse and the electron pulse was estimated from the mea-
surement using a streak camera (C1370, Hamamatsu Photonics Co. Ltd.), because the jitter
is one of important factors that decide the time resolution of the pulse radiolysis. The jitter
was several picoseconds. To avoid eects of the jitter on the time resolution, a jitter com-
pensation system was designed [74]. The time interval between the electron pulse (Cerenkov
light) and the laser pulse was measured by the streak camera at every shot. The Cerenkov
radiation was induced by the electron pulse in air at the end of the beamline. The laser pulse
was separated from the analyzing light by a half mirror. The precious time interval could be
Figure 12 The subpicosecond pulse radiolysis system.
obtained by the analysis of the streak image. All equipment described above was controlled
by a personal computer. The acquisition time was 1 sec per one shot. Fig. 8 shows the time-
dependent behavior of the absorption due to hydrated electrons at the wavelength of 780
nm was observed in distilled and deaerated water in a quartz cell with the optical length of
2.0 mm [76]. Fig. 8 shows the time-dependent behavior of the hydrated electron obtained in
the system. The solid line represents the tting curve for the experimental data. The 10
90% rise time is 2.0 psec.
The time resolution of the stroboscopic pulse radiolysis depends on the width of
electron pulse and that of laser. In this experiment, both widths are much shorter than 2.0
psec. Furthermore, the time resolution is limited by the dierence between the velocity of
the light and that of the electron pulse in the sample. The passing time of the electron pulse
through a sample is given by L/(bc), where L is an optical length of a sample, b is the ratio
of the velocity of electron to that of light in the vacuum, and c is the velocity of light in the
vacuum. On the other hand, in the case of light, the passing time is given by Ln/c, where n
is a refractive index of a sample. Therefore the time resolution limited by the thickness of
the sample is 1.8 psec (1090% rise time) at n=1.33 and 1=2 mm. Therefore the 1090%
rise time of 2.0 psec is the time resolution of the system. In the present system, the time
resolution is mainly limited by the thickness of the sample. The time resolution of 800 fsec
can be obtained by a quartz cell with the optical length of 0.5 mm as shown in Fig. 9. The
S/N ratio decreases with the optical length decreases. So the S/N ratio is not good for a
0.5-mm cell.
As discussed above, it is necessary to use a thin sample in high time resolution pulse
radiolysis. The use of a thin sample leads to the degradation of the S/N ratio because the
signal intensity is proportional to the optical length of the sample. In pulse radiolysis
experiments, the optical density is generally calculated based on the intensity of the probe
light passing through a sample with an electron beam present (I ) and that of the probe
light passing through a sample with the electron beam absent (I
0
).
O:D: log
I
0
I
44
If there is no uctuation of laser intensity, we have to measure I
0
only once. Actually,
the envelope of laser pulses changes in a relatively long time range (typically from several
minutes to a few tens of minutes) because of the change of environmental factors such as
room temperature and coolant temperature. There is also an intensity jitter caused by
factors such as the mechanical vibration of mirrors and the timing jitter of electronics.
Furthermore, in our system, the laser system is located about 15 m from the beam port to
prevent radiation damage to the laser system. (Later, it was moved into a clean room,
which was installed in the control room to keep the room temperature constant and to
keep the laser system clean. The distance is about 10 m.) Therefore it is predicted that a
slight tilt of a mirror placed upstream will cause a displacement of the laser pulse at the
downstream position where the photodetector is placed.
From Eq. (44), to achieve a good S/N ratio measurement, it is necessary and
sucient to lower the uctuation of I
0
/I. Based on this information, we devised a new
method to measure I and I
0
with a good S/N ratio. We named it the double-pulse
method. In the new method, I
0
is measured by the laser pulse passing just before the laser
pulse used to measure I. Because the frequency of the Ti:Sapphire laser is 81 MHz, the
time interval of two laser pulses is 12.3 nsec. The laser pulse for the measurement of I
passes through the sample 12.3 nsec after the laser pulse for the measurement of I
0
. An
electron pulse enters the sample between two laser pulses. The two laser pulses are
expected not to suer from the vibration of optical elements because it is thought that the
frequency of mechanical vibration mainly caused by the vibration of coolant and
ventilator systems is lower than the MHz order. The uctuation of I
0
/I is measured at
the position where the photodetector is located. The uctuation of I
0
/I is reduced from
5.34% to 0.80% using the newly developed method. The time-dependent behavior of
geminate ion recombination in neat dodecane is shown in Fig. 10 as a typical example that
demonstrates the eect of the newly developed system. The sample was deaerated by Ar
bubbling in a quartz cell having an optical length of 2.0 mm and was irradiated at room
temperature. The high S/N data obtained by the improved subpicosecond pulse radiolysis
using the double-pulse method makes possible the detailed studies on the geminate
recombination of electrons and radical cations. The details of the time-dependent behavior
of the geminate recombination shown in Fig. 10 are discussed in the next section.
2.3. Experimental Studies of the Kinetics of Geminate Ion Recombination
Kinetics of Geminate Ion Recombination
The early work of the kinetics of geminate ion recombination studied by picosecond pulse
radiolysis has been briey reviewed [78]. The studies on the kinetics of geminate ion
recombination in liquid hydrocarbons were dicult because the very high time-resolved
spectroscopy is indispensable for monitoring the time behavior of the geminate ion re-
combination. The combination of the picosecond single electron bunch with streak cameras,
independently developed in 1979 at Argonne National Laboratory [55] and at the University
of Tokyo by us [56], enabled the time behavior of recombination uorescence of the
geminate ions. The direct measurement of the recombination uorescence produced by
geminate ion pairs [55,57] stimulated studies on the kinetics of the geminate ion recombi-
nation and gave us many kinds of the problems for understanding the geminate kinetics and
the positive ions in irradiated hydrocarbons. But the recombination uorescence is the
indirect measurement of the geminate positive ions and is unable to make clear the details of
both the identication and characteristics of positive ions in irradiated hydrocarbons,
especially cyclohexane [79].
The picosecond pulse radiolysis system in the combination of very fast response
photodiode with the transient digitizer (the time resolution of about 800 psec) was devel-
oped by us in 1982 [60]. This system was the rst picosecond pulse radiolysis system that
could measure the kinetics of ions and triplet states on subnanosecond timescale by using
only one picosecond single bunch electron pulse. This system has no limitation of nano-
and microsecond timescale measurement and the radiation damage of the samples by this
system was much less than that by other preceding picosecond pulse radiolysis. The change
of the ratio of the formation rate of the solute excited triplet state to the decay rate of the
solute anion observed directly by this system showed the loss process of the spin cor-
relation of geminate ion pairs very clearly in the time range between 5 and 20 nsec [60].
The decay of the geminate ion pairs in cyclohexane [62] was analytically analyzed by the
Smoluchowski equation [13] and in various nonpolar solutions [63] on the basis of the
absorption of solute ions in time range from 800 psec to several hundred nanoseconds by
using the same system. In 1987 [64], the kinetics of the geminate pairs of solute ions was
analytically analyzed in the time range from 50 psec to several hundred nsec by the extend
Smoluchowski equation [68] on the basis of the combination of the picosecond pulse
radiolysis system composed of very fast response photodiode and the transient digitizer
[60] with the specially designed picosecond pulse radiolysis system composed of a streak
camera [67]. Then, geminate ion recombination and the formation process of solute ex-
cited states in cyclohexane solutions of biphenyl observed by the combination of two types
of picosecond pulse radiolysis with emission [56] and absorption [60] spectroscopy were
analyzed by the expansion of the extended Smoluchowski equation to the formation of
solute excited states [65]. The comparison of the theoretical treatment based on Smolu-
chowski equation with the absorption and emission data on the geminate recombination
of solute ions and the formation of solute excited states on timescale from 50 psec to
several hundred was successfully achieved [64,65].
Now we shall discuss about the geminate recombination of electrons and solvent
cation radical in liquid hydrocarbons. The original stroboscopic pulse radiolysis in
Argonne National Laboratory [54] was unable to make good quality measurements on
geminate recombination of the electron and the positive ion in liquid hydrocarbons. In
1983, the modication of the Argonne linac made possible the rst good quality measure-
ments of the weak absorption at 600 nm in neat liquid n-hexane and cyclohexane. The
transient absorptions at 600 nm are assigned to the positive ion and the excited state for
neat n-hexane and cyclohexane, respectively [79]. The dierence between broad absorption
bands of the excited states and the radical cations become larger with increasing the
number of carbon atoms of n-alkanes, although the peak wavelengths of both absorption
bands become longer with increasing the number of carbon atoms of n-alkanes [66]. The
lifetimes of alkane radical cations become shorter with decreasing the number of carbon
atoms of n-alkanes. In irradiated neat cyclohexane, very broad visible absorption bands,
mainly because of the excited state, were observed [66]. Although radiolysis of cyclohexane
and n-hexane was heavily studied, both experimentally and theoretically, the kinetics of
radical cations of both cyclohexane and n-hexane are dicult to be studied because of
their very short lifetimes [66], the absorption overlapping of radical cations and excited
states [66], and the complexity of their reactions and characters [80]. Because the
complication of the absorption spectroscopy on radical cations of smaller hydrocarbons
was clearly shown experimentally [66], the absorption spectroscopy of the geminate
recombination of electrons and cation radicals in liquid hydrocarbons has mainly been
carried out for higher n-alkanes such as n-dodecane instead of both cyclohexane and n-
hexane.
Because the LL twin picosecond pulse system with the laser diode as monitor light
enabled the absorption spectroscopy from visible to infrared region for the rst time in
picosecond pulse radiolysis, the kinetics of the geminate recombination of both electrons
and cation radicals were rst measured on picosecond timescale in the same sample and
agree with each other on picosecond timescale from 50 psec after a pulse [71]. By using the
laser synchronized picosecond pulse radiolysis [73] with the higher S/N ratio than that of
the LL twin system, the good agreement of the diusion theory with experimental data
were conrmed on a picosecond timescale from 50 psec after a pulse, but a slight dierence
between the experimental data and the simulation based on Smoluchowski equation using
the exponential function of the initial separation between electrons and radical cations
[81]. Many factors from the time resolution of the system and simulation models are
considered as the reason for the dierence. Because the time resolution and S/N ratio of
the laser synchronized subpicosecond pulse radiolysis was drastically improved by both
the jitter compensation system [74] and the double-pulse method [77] as described above,
the dierence between the experimental data and the simulation based on Smoluchowski
equation using the simple model was clearly observed on timescale within 50 psec. The
details of the kinetics of the geminate ion recombination studied by the laser synchronized
subpicosecond pulse radiolysis are described in the next section.
Subpicosecond Pulse-Radiolysis Studies of Geminate Ion Recombination
The kinetics data of the geminate ion recombination in irradiated liquid hydrocarbons
obtained by the subpicosecond pulse radiolysis was analyzed by Monte Carlo simulation
based on the diusion in an electric eld [77,81,82]. The simulation data were convoluted
by the response function and tted to the experimental data. By transforming the time-
dependent behavior of cation radicals to the distribution function of cation radicalelectron
distance, the time-dependent distribution was obtained. Subsequently, the relationship be-
tween the space resolution and the space distribution of ionic species was discussed. The
space distribution of reactive intermediates produced by radiation is very important for
advanced science and technology using ionizing radiation such as nanolithography and
nanotechnology [77,82].
The deposited energy of radiation is spent mostly for ionization of liquid hydro-
carbon molecules. During ionization, a pair of a cation radical (RH
+
) and an electron
(e
) is produced as follows,
RH
a
RH
45
After the ionization, the electrons with excess energy interact with surrounding molecules
and become thermalized. The reaction from the ionization to thermalization is estimated
to occur within about 1 psec. The initial separation length between the cation radical and
the thermalized electron is several nanometers on average.
In nonpolar materials, most of the electrons recombine with the counter cation
radicals as shown by Eq. (46). RH* is one of the main products produced through the
recombination.
RH
a
RH* 46
This occurs because the initial separation length between the cation radical and the
electron is smaller than the Onsager length (r
c
) at which the thermal energy of an electron
corresponds to the Coulomb eld. This reaction is called the geminate ion recombination
and has been investigated by many researchers globally.
The experimental method and apparatus, and a procedure of the Monte Carlo method
that simulates the geminate ion recombination are described, and the time-dependent
distribution is elucidated.
The experiments were carried out using the subpicosecond pulse radiolysis system
[77] described in Sec. 10.2.2 (Subpicosecond Pulse Radiolysis). Considering the signal
intensity and the degradation of the time resolution, a sample cell with the optical length
of 2 mm was mostly used. The sample was saturated by Ar gas to eliminate the scavenging
eect by the remaining O
2
gas.
At the initial stage of reactions, the produced intermediate species such as the cation
radical and the electron exist in a narrow space, the so-called spur. After the electron
thermalization process, a pair of a cation radical and a thermalized electron remain in a
spur. The geminate ion recombination of the cation radical and the electron occurs before
these ionic species diuse and spread uniformly in the media. Therefore the geminate ion
recombination takes place in the spur. On the condition of a so-called single pair model,
the reaction, which is described by the following equation, can be solved in spherical co-
ordinates with a radial component.
Bwr; t
Bt
D j
2
wr; t
1
k
B
T
jwr; tjVr
_ _
2
Hong and Noolandi [11,13,83] analytically solved Eq. (2) under the following initial and
boundary conditions:
wr; 0 fr initial condition 47
wR; t 0 boundary condition 11a
Equation 2 indicates that if the distance r between the cation radical and the electron
becomes less than the reaction radius R, they recombine. The typical shape of f(r,r
0
), the
initial distribution function, is expressed by the following exponential or Gaussian.
fr; r
0

1
r
0
exp
r
r
0
_ _
exponential 19
fr; r
0

4r
2
p
p
r
3
0
exp
r
2
r
2
0
_ _
gaussian 20
The solution of Eq. (2) can also be obtained by a numerical analysis similar to the calculus
of nite dierences. However, an analytical or semianalytical method based on Eq. (2) is
not suitable for discussing the time-dependent distribution function because the calcu-
lation is lengthy.
On the other hand, the Monte Carlo method enables us to simultaneously obtain the
time-dependent decay curve and the time-dependent distribution function. Therefore we
adopted Monte Carlo simulation [18,21,84,85] for the analysis. The geminate ion
recombination is also described as follows,
Dr
i

6D
i
Dtn
i
_
l
i
DtE
i
48
In Eq. (48), i represents the cation radical and electron. The D
i
and l
i
are the diusion
constant and the mobility of the ith species, respectively. The relationship between them is
described by the Einsteins relation. The calculation was carried out in the rectangular
coordinates (x, y, z). For each time step Dt, the vector of movement Dr
i
is calculated
according to Eq. (48). The rst term in Eq. (48) represents the diusion component. It was
calculated by uniform random variables n
i
ranging from 1 to 1. The second term in Eq.
(48) represents the drift in the electric eld E
i
, which is due to counter ionic species. At rst,
the cation radical and the electron were set at (0, 0, 0) and (x
0
, 0, 0) in the coordinates,
respectively. Therefore x
0
corresponds to r
0
, which is the initial separation length between
the cation radical and the electron. After that, the positions of the ith species were
calculated by Eq. (48). If the distance between the cation radical and electron became less
than the reaction radius (R), they recombine. The time taken for the recombination was
recorded. The Dt was taken to be 0.1 psec. By carrying out calculations for 4000 pairs of the
cation radical and the electron, the survival probability of the cation radicals was obtained.
The time-dependent distribution function was also obtained by recording the distance
between the cation radical and the electron. Before analyzing the experimental data, to
check the validity of the simulation code, we compared the simulation data with the
analytical solution given by Hong and Noolandi [11,13,83]. The calculation was completed
in about 15 min by a personal computer. The result is shown in Fig. 13(a). The initial
distribution function and the Onsager length (r
c
) were taken as a delta function d(rr
0
) of
r
0
=7.5 nm and r
c
=30 nm, respectively. The dots and the solid line represent the analytical
solution and the simulation curve, respectively. They perfectly agree with each other.
Therefore the validity of the code was conrmed. At the same time, the time-dependent
distribution function was obtained. It is shown in Fig.13(b). The vertical axis and the
horizontal axis represent the probability density and the distance between the cation radical
and the electron, respectively. The probability density is dened as the existing ratio of
species per unit length. We can see that the electron, which existed at r
0
=7.5 nm, diuses
and recombines with the cation radicals.
In the experiment, liquid n-dodecane was used due to the small overlap among
intermediate species. At the wavelength of the Ti:Sapphire fundamental light, a large part
of the absorption is assigned to the cation radicals in n-dodecane [66]. Thus the decay
curve of the experimental result shows a decay of the cation radicals indicated in Eq. (46).
Fig. 14(a) shows the time-dependent behavior of the cation radicals in liquid n-dodecane,
which was obtained by the subpicosecond pulse radiolysis and monitored at 790 nm [82].
The vertical axis represents optical density, which is proportional to the density of the
intermediate species. The dotted and the solid lines represent the experimental curve and
the simulation curve, respectively. It was observed that the cation radicals began to be
produced at time zero and decayed by the recombination. The rise time of the exper-
imental data corresponded to the time resolution of the measurement system. In the
simulation, the parameters of the electron diusion coecient (D
e
) =6.4 10
4
cm
2
/sec,
the cation radical diusion coecient (D
+
) =6.0 10
6
cm
2
/sec, the relative dielectric
constant e =2.01, the reaction radius R=0.5 nm and the exponential function as shown
in Eq. (19) with r
0
=6.6 nm were used. These values are the same as those used in previous
papers [81,86]. The exponential distribution function was realized by using the rejection
method with two sets of uniform random variables. The shape and mean value of the
initial distribution function are dependent on the materials used. The obtained simulation
curve was convoluted by the response function [77] and tted to the experimental curve so
that the residual between two curves was minimized in the long timescale. Although the
Figure 13 (a) Comparison of the simulation curve with the analytical solution given by Hong and
Noolandi [11,13,83]. The initial distribution function and the Onsager length (r
c
) were taken as a
delta function d(rr
0
) of r
0
=7.5 nm and r
c
=30 nm, respectively. The dots and the solid line
indicate the analytical solution and the simulation curve, respectively. (b) Time-dependent
distribution function that was obtained from the simulation of (a). r indicates the distance between
the cation radical and the electron.
time range was terminated at 350 psec in Fig. 14(b), it was conrmed that the experimental
curve is in accordance with the simulation curve in the nanosecond timescale [63,66,81,86].
As a result, the two curves corresponded with each other after a time interval of about 50
psec after irradiation. Some factors that may explain the disagreements within the time
interval of about 50 psec are discussed but was not determined [81]. Fig. 14(b) shows the
time-dependent distribution obtained by the simulation curve in Fig. 14(a). The solid line,
dashed line, and dots represent the distribution of cation radical-electrons distance at 0,
30, and 100 psec after irradiation, respectively. At 0 psec, the distribution was in the shape
of the exponential function. At 30 psec, a large part of the electrons, especially near the
cation radical, have already recombined. At 100 psec, the shape of the distribution curve is
highly similar to that of 30 psec.
The space distribution of ionic species, which move in several or a few nanometers
scale, should not be ignored in future nanolithography and nanotechnology based on beam
technology.
Further detailed kinetics of the geminate recombination of electrons and positive ions
and their application to the advanced technology will be studied by higher time resolution of
the femtosecond pulse radiolysis and both by the higher S/Nratio and the wider wavelength
monitoring light of the improved subpicosecond pulse radiolysis shown in Fig. 7.
3. EXPERIMENTAL STUDIES OF ELECTRONION BULK RECOMBINATION
IN CONDENSED MATTER
3.1. Introduction
The investigation of the dynamic behavior of low-energy electrons such as electron transport
and reactivities in nonpolar dense molecular media is of essential importance in both
Figure 14 (a) Time-dependent behavior of cation radicals in liquid n-dodecane monitored at 790
nm. The dotted and the solid lines represent the experimental curve and the simulation curve,
respectively. The parameters of the electron diusion coecient (D
e
) =6.4 10
4
cm
2
/sec, the cation
radical diusion coecient (D
+
) =6.0 10
6
cm
2
/sec, the relative dielectric constant e =2.01, the
reaction radius R=0.5 nm, and the exponential function as shown in Eq. (19) with r
0
=6.6 nm were
used. (b) Time-dependent distribution function obtained from tting curve of (a). r indicates the
distance between the cation radical and the electron. The solid line, dashed line, and dots represent the
distribution of cation radicalelectron distance at 0, 30, and 100 psec after irradiation, respectively.
fundamental and applied sciences [87100]. The values of an electron mobility l
e
have been
extensively measured in a variety of these media, and several theoretical models have been
proposed for the transport mechanism. Electron reactivities with solute molecules or
positive ions in these media have been also extensively investigated. The former reaction
is electron attachment and the latter electronion recombination. The investigation of these
electron reactivities has provided a new insight into that of the behavior of low-energy
electrons in matter.
In the following, a brief survey is given of the experimental investigation of electron
ion recombination with particular emphasis placed on the comparison between the
experimental and theoretical results as well as on that between the results in dense media
and in low-density gases or beams.
A survey of electron attachment with a similar emphasis has been given elsewhere
[92,100].
3.2. Comparative Aspects of ElectronIon Recombination Processes
in the Gas and Condensed Phases
It is of great interest to investigate the electronion recombination in dense molecular
media in the density range from dense gases to liquids and solids [96,97,99,100] because the
Coulombic interaction distance between an electron and an ion, as expressed by the
Onsager length r
c
, which is given by Eq. (1), is much bigger than the mean intermolecular
distance of the nearest neighbor molecules in the medium.
Electronion recombination processes in isolated two-body collisions in beams or in
low-pressure gases have been extensively studied mainly with a merged beam method
[101], a pulsed afterglow method [102], a owing afterglow method [103], and a recently
developed method by means of a cooler ring [104,105]. Cross sections or rate constants for
electronion recombination obtained by these experimental methods are theoretically
explained by the mechanism including molecular superexcited states as collision complex
or reaction intermediate species. Spectroscopy and dynamics studies of molecular super-
excited states have been recently in great progress [106,107], and these states are assigned
mainly to vibrationally, doubly, or inner-core excited molecular high Rydberg states
converging to each of ion states.
In the gas phase at one to several atmospheric pressures, electronion recombination
processes have been studied with a pulse-radiolysis method, and observed recombination
rate constants k
r
are expressed by,
k
r
k
2
k
3
n 49
where k
2
and k
3
are the two-body and three-body rate coecients, respectively, and n is the
density of a third-body molecule. The magnitude of observed rate constant values is ex-
plicable in terms of the collisional de-excitation of two-body formed complex or inter-
mediate species.
3.3. Experimental Methods to Measure Absolute Rate Constants
for Recombination
However, in dense media such as high-pressure gases near the critical points, liquids, and
solids, experimental studies were relatively few because of diculties in experimental
methods. But recently there has been great progress due to the development of a new
powerful method, called the decay-curve analysis method [96,97,99,100]. The following are
a brief comparative survey of the experimental methods [99].
1. In a pulse-radiolysis d.c. conductivity method, k
r
/l
e
is measured and then k
r
is
determined from the measured k
r
/l
e
and a separately known l
e
.
2. In a pulse-radiolysis charge-clearing method, a residual amount of charge that is
left unrecombined is collected and measured. Because the collected charge is
expressed as a function of k
r
, the value of k
r
/bl
e
, where b is a correction factor due
to a space charge is obtained. The kr value is thus determined by using the value of
l
e
known separately and the value of b which is approximately assumed.
3. In a pulse-radiolysis optical-absorption method, the value of k
r
/e, where e is a
molar absorption coecient, is measured by the time-resolved measurement of
the optical absorption of solvated electrons, and then the k
r
value is determined
by the observed value of k
r
/e and the value of e known separately.
4. In a pulse-radiolysis d.c. conductivity method with a long pulse width, the
resulting steady state current during the long pulse is considered by the
assumption that the rate of excess electron generation becomes equal to the rate
of electron loss because of the reaction with positive ions and impurities.
5. In a pulse-radiolysis microwave-conductivity method, the k
r
value is determined
by the time-resolved measurement of microwave conductivity.
6. In a method using a radioisotope, e.g.,
207
Bi, as an internal radiation source, the
dierence in a uorescence intensity with and without a d.c. electric eld is
assumed to be due to electronion recombination, and the k
r
value is determined
by the time-resolved measurement of the uorescence with the known number
density of ionization, which is separately determined.
7. In the decay-curve analysis method, which is one of the pulse radiolysis d.c.
conductivity methods, both k
r
and l
e
values are simultaneously determined by
analyzing observed transient current decay curves by tting them to a general
formula of conductivity both at a high pulse dose of x-rays where the
recombination is predominant and at a low pulse dose where the recombination
is negligible. This is a useful method also because of the k
r
determination without
knowing the pulse dose of x-rays or the free-ion yield. Recently, this method has
been improved by taking account of a space-charge eect to obtain more
accurate values of k
r
.
3.4. Experimental Results: The Breakdown of the Debye Theory
In the liquid phase, observed electronion recombination rate constants k
r
in a variety of
nonpolar media were, as shown in Fig. 15, in good agreement with the values of k
D
calculated from the reduced Debye equation,
k
D

4pe
e
l
e
50
viz., Eq. (36b), in the range of l
e
below about 150 cm
2
/V sec, and thus the recombination
in these media was concluded to be diusion controlled [99,100,112].
However, in liquid and high-pressure gaseous methane in which most l
e
values are
larger than 150 cm
2
/V sec, it has been found [49] that the observed k
r
values are much
lower than k
D
. This experiment has stimulated a great deal of theoretical investigations
[24,25,30,3842,48,113119] of the recombination process in dense media. Because the
magnitudes of the electron mobilities in dense Ar, Kr, and Xe media are as high as in dense
methane media, the values of k
r
and l
e
in these media have been also measured [120123]
and compared further with theoretical results. The observed k
r
values in these rare-gas
media in both liquid and dense gas phases are again found to be much smaller than those
calculated by the reduced Debye equation. However, in the solid phase, the observed
k
r
values are almost in agreement with those calculated by Eq. (50). These results are
summarized in Fig. 16. The eect of an external d.c. electric eld strength on both k
r
and l
e
values has also been measured. An example of the eld eect is shown in Fig. 17 for liquid
Ar. Recently, the eect of the addition of molecular impurities such as N
2
and CH
4
on k
r
and l
e
values has been further examined to dierentiate between the energy and spatial
criteria [39,42,114] in expectation that electrons heated up by applied external electric elds
may be cooled down by the added molecular impurities due to inelastic collisions between
electrons and molecules. Detailed comparisons have been made between these experimental
results and the theoretical ones, from which it has been concluded that the recombination
in liquid and dense gaseous Ar, Kr, and Xe as well as CH
4
is clearly dierent from a usual
diusion-controlled reaction corresponding to Eq. (50).
3.5. Comparison with Theories
Theoretical investigations trying to explain the k
r
deviation from k
D
, i.e., the breakdown
of the Debye theory, are summarized as follows:
1. A semiempirical treatment taking both the diusion controlled and electron-
energy exchange controlled recombination processes into account [38].
2. A Monte Carlo simulation with the parameter K/a, where K is the mean free path
of electrons and a is the reaction radius [39,42,114].
Figure 15 Variation of k
r
with l
e
in the l
e
region below about 150 cm
2
/V sec in condensed
nonpolar media. n-Pentane, n-hexane, TMS (5); n-hexane, cyclohexane (); neopentanen-hexane
mixtures (.); and liquid and solid neopentane (o). The straight line corresponds to k
D
(From Refs.
99,100,112.)
Figure 16 Variation of k
r
/k
D
with l
e
in condensed nonpolar media [99,100,112]. Neopentane, liquid
(D) and solid (E); neohexane (z); TMS (q); n-pentane, n-hexane (+); n-hexane, cyclohexane (5);
neopentanen-hexane mixtures (); methane, liquid (.) and solid (n); and argon, liquid (o) and solid
( w ).
Figure 17 Electric eld dependence of k
r
(.) and nl
e
(o) in liquid argon (T=87 K, n = 2.1 10
22
/
cm
3
) (From Refs. 99,100,120.)
3. A molecular dynamics simulation [115].
4. A fractal treatment [24,117,118].
5. A gas kinetic approach [116].
6. An approach based on the FokkerPlanck equation [40].
7. Theories to explain the eect of applied external electric elds on k
r
[30,48,119].
Warman [38] rst proposed a semiempirical formula of the recombination rate
constant to explain the new experimental result of k
r
<<k
D
[49]. In spite of many as-
sumptions to derive the formula, the calculated value for liquid argon is in rather good
agreement with the experimental one. However, for dense gaseous argon, the calculated
value is far from the experimental one. Tachiya [39,42,114] pointed out using a Monte
Carlo method that if K/a is not negligible the rate constant for bulk recombination
deviates from k
D
. Experimental k
r
values for liquid methane lie around the theoretical
curve of his simulation which uses K/a only as a parameter. He also explains the eect of
the eld strength on k
r
. The values of k
r
roughly increase in proportion to the eld strength
in the lower eld strength region and form a peak at around the critical eld strength.
These results are explained in terms of the eect of the eld strength on the trajectory of
electrons to be recombined. In the lower eld region, the disentangling of random electron
trajectories caused by the presence of the external electric eld should increase the k
r
value.
In the eld region higher than the critical eld strength, the internal energy of an electron
ion pair decreases the k
r
value.
Recent experiments [123] on the eects of electric eld strength and the addition of
molecular impurities on k
r
values in dense gaseous Ar and Kr at the density range near the
critical points, in which a new experimental method to measure k
r
values are developed by
including the eect of space charges on k
r
and l
e
values in the analysis of observed
conductivity signals, have clearly shown again a large deviation of k
r
values from the
Debye theory. The obtained experimental results are discussed in terms of the electron
mean free paths and electron energies based on recent theories.
It is concluded that electronion recombination processes in dense high-mobility
media such as liquid and dense gaseous Ar, Kr, and Xe as well as CH
4
are clearly dierent
from those expressed by the Debye theory, i.e., a well-established diusion-controlled
theory. Newly developed theories, instead of the Debye theory, as stimulated by the
experimental nding of the breakdown of the Debye theory, have been explicable, at least
qualitatively, in terms of the experimental results of the breakdown, i.e., k
r
<<k
D
, but still
quantitatively inexplicable not only in the magnitude of the breakdown itself but also in
the eects of external electric elds and the addition of molecular impurities on it. Further
new investigations are strongly needed both theoretically and experimentally. It is also
noted that these investigations may provide a new insight into the fundamental processes
of phenomena of ionization and excitation in condensed matter, e.g., those in liquid xenon
detectors [124].
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11
Radical Ions in Liquids
Ilya A. Shkrob and Myran C. Sauer, Jr.
Argonne National Laboratory, Argonne, Illinois, U.S.A.
1. INTRODUCTION
The interaction of ionizing radiationfast electrons, a-particles, x- and g-rays, and
ultraviolet (UV) and vacuumultraviolet (VUV) photonswith molecular solids and liquids
causes the formation of short-lived electron-hole pairs that, in such media, thermalize and,
eventually, localize yielding radical ions and/or trapped (solvated) electrons and holes (see
Chaps. 15). The distinction between the radical anions and the solvated electrons is
arbitrary. For the time being, it will be assumed that radical ions have an excess electron
or electron deciency in the valence orbitals of a single solvent molecule (molecular ions
or monomer ions) or a small group of such molecules (dimer ions or multimer ions)
that do not share charge with neutral solvent molecules that solvate them. Naturally, the
excess electron in a radical anion is indistinguishable from other valence electrons in this
anion. By contrast, in the solvated electron (also known as cavity electron, see Chap.
7), the electron density resides mainly in interstitial sites between the solvent molecules
(solvation cavity) that are polarized by the negative charge at its center (thereby forming
the outer shell of a negative polaron). The underlying assumption of this visualization is
that the solvated electron is a single-electron state whose properties can be given by a band
model in which the valence electrons in the solvent and the excess electron in the cavity are
wholly separately treated [1]in the exact opposite way to how the electronic structure of
the solvent radical ion is viewed. An additional assumption is usually made that the excess
electron interacts with (rigid, exible, or polarizable) solvent molecules by means of an
empirical classical potential. Both of these simplifying assumptions nd little support in
structural studies of trapped electrons in vitreous molecular solids using magnetic res-
onance spectroscopy [2].
The primary speciessolvated/trapped electrons/holes and solvent radical ions
are ecient donors and acceptors of electrons and protons; they readily react with the
solvent, with the solute and dopant molecules, with each other, and with the short-lived
species (radicals, molecular fragments, and excited states) generated in the ionization and
excitation events along with these primary charges. In most radiation chemistry studies,
the species of interest are the resulting secondary ions, radicals, and excited neutrals.
For example, radiolysis of liquid solutions and doped solid matrices is widely used for
producing high yields of secondary radical ions (via ionmolecule reactions of the primary
ions) for detailed structural studies, e.g., by using magnetic resonance and UVVis and/or
infrared (IR)-Raman spectroscopies [3]. The general approach in these structural studies is
to generate a primary ion that rapidly reacts with a dopant (or solute) of interest yielding a
secondary ion that is relatively stable in the matrix (on the time scale of observation). Such
stabilization usually requires reduced mobility (low sample temperature), low reactivity,
and high ionization potential (IP) or electron anity (EA) of the solvent/matrix relative to
the solute. A classical example of the matrix stabilization is radiolytic generation of
hydrocarbon radical cations in frozen halocarbon (freon) solutions [3,4]. Rapid dissocia-
tive electron attachment to the halocarbon solvent yields relatively immobile halide anions
and C-centered radicals that recombine slowly (if at all) in these low-temperature matrices
[3]. The solute radical cations are rapidly formed (on the time scale of the observations)
because of the oxidation of the dopant by a mobile solvent hole [3]. As a result, the ionization
energy is eciently converted into the product (radical cation), enabling many types of
structural studies. A similar approach is used for stabilization of radical cations in rare gas
matrices doped by SF
6
(a matrix favored by IR-Raman spectroscopists [5]), zeolites, and
microporous solids (favored by electron paramagnetic resonance (EPR) spectroscopists [6]),
etc. A review of the literature shows that almost a third of radiolytic studies on organic
radical ions are done in this fashion.
Another popular approach is to react the intermediates of liquid water radiolysis
hydroxyl radicals and hydrated electronswith the parent molecules of interest (see
several representative reviews in Ref. 7). The resulting solute radical ions are observed in a
time-resolved fashion, using pulse radiolysistransient absorption spectroscopy with
nanosecond-to-millisecond time resolution; other detection techniques may involve uo-
rescence, time-resolved EPR, and Raman spectroscopy. The emphasis in such studies is to
observe structural rearrangements and reaction patterns of short-lived solute radical ions.
The reaction behavior is usually complex (ring opening, protonation/deprotonation,
rearrangements, etc.), especially for radical ions whose parent molecules are multifunc-
tional organic compounds, such as biomolecules and biomimetic systems (see, e.g., Chap.
15). Whether the solute is simple (inorganic ions) or complex (biomolecules), the general
approach stays the same. A variation of this common technique is pulse radiolysis of
solutes in aprotic, high-IP liquids, such as acetone, CC
l4
, CH
2
Cl
2
, 1,2-dichloroethane, and,
most often, n-butyl chloride [8]. Unlike the OH radicals in water, solvent holes in such
liquids oxidize almost any organic solute; the resulting secondary cations are usually more
stable than the same species in water, for lack of ecient donors and acceptors of the
proton. There are many examples of using this approach for studies of radical cations of
hydrocarbons, heterocyclic compounds, phenols, etc.
Finally, solute radical ions can be generated by light-induced, one-photon or multi-
photon ionization of their parent compounds (Chaps. 5 and 16). This approach is par-
ticularly useful in the ultrafast studies of short-lived, unstable radical ions that aim to
unravel their solvation, recombination, reaction, and vibrational relaxation dynamics of
the primary charges (see, e.g., Chap. 10). Whereas the time scale of radiolytic production
of secondary ions is always limited by the rate with which the primary species reacts with
the dispersed parent molecules, light-induced charge separation can occur in <100 fsec.
There are many studies on photoionization of solute molecules in liquid solutions; we do
not intend to review these works.
There are also many photoreactions, in which rapid, ecient charge transfer between
electron donor and acceptor moieties occurs, yielding a radical ion pair that subsequently
dissociates; because the solvent is not oxidized or reduced in these light-induced reactions,
these reactions belong to photo- rather than radiation chemistry. Of particular interest, in
the context of radiation chemistry studies, are photoreactions in which the solvent is
oxidized and the resulting hole reacts with the solutes yielding secondary radical ions, just
like in radiolysis. This occurs, for example, in one-photon excitation of certain salts (such
as N-methyl quinolinium pentauoride) in low-IP nonpolar uids (benzene and toluene)
[9,10,11]. Upon photoexcitation, the cation moiety accepts a valence electron from the
solvent, and the resulting dimer radical cation of the solvent reacts with solute molecules.
This reaction is so ecient that it has been used for preparative organic synthesis [9].
Similar photooxidation reactions of aliphatic alcohols, by excited transition metal (e.g.,
Fe
III
) [10] or stable organic cations (e.g., methylviologen
2+
) [11], have been studied.
Another class of photooxidation reactions mimicking radiolytic reactions involves elec-
tronically excited radical cations [12,13]. Radical cations are more ecient oxidizers than
stable cations because they are closer in energy to the valence band of the solvent.
Photoexcited aromatic radical cations (IR to UV) readily oxidize most solvents, including
saturated hydrocarbons [12], water, and alcohols [13]. These charge-transfer-from-solvent
(CTFS) photoreactions mirror the better-known charge-transfer-to-solvent (CTTS) reac-
tions in which photoexcited anion (e.g., halide) injects an electron into a polar liquid [14].
The photoelectrons released in the CTTS or photoionization reactions can be used to
generate secondary radical anions, although this approach is seldom used in practice.
Understandably, most workers who use radiolysis, photoionization, CTFS, or CTTS
as the means for generation of (secondary) radical ions pay little attention to the nature of
short-lived precursors of these ions. After all, the subject of interest is a secondary rather
than a primary ion. This ad hoc approach is justiable because radiolytic production is
just another means of obtaining a sucient yield of the radical ion. Quite often in such
studies, the radiolysis is complemented by other techniques for radical ion generation,
such as plasma oxidation, electron bombardmentmatrix deposition, and chemical and
electrochemical reduction or oxidation. While the data obtained in these studies are useful,
there is little radiation chemistry in suchnominally, radiation chemistrystudies.
There are many excellent books and reviews on the structure and reactions of
secondary radical ions generated in radiolytic and photolytic reactions. Common topics
include the means and kinetics of radical ion production, techniques for matrix stabiliza-
tion, electronic and atomic structure, ionmolecule reactions, structural rearrangements,
etc. On the other hand, the studies of primary radical ions, viz. solvent radical ions, have
not been reviewed in a systematic fashion. In this chapter, we attempt to close this gap. To
this end, we will concentrate on a few better-characterized systems. (There have been many
scattered pulse radiolysis studies of organic solvents; most of these studies are inconclusive
as to the nature of the primary species.)
Before we review specic systems, note that the primary species should be considered
on a dierent footing than the secondary radical ions. The latter ions are well isolated
from their parent molecules by the matrix or the solvent. By contrast, in the primary
species, the charge is residing on a molecule(s) that is surrounded by like solvent
molecules. This often results in unusual properties because the barriers for charge hopping
and charge delocalization are lowered. We will examine several examples of the reaction
and migration dynamics of such primary radical ions; the multiplicity of examples and
commonality of the observed behavior suggest a general pattern.
As demonstrated below, a primary charge viewed as a solvated electron or the mo-
lecular ion residing in an inert liquid does not account for experimental observations in
many, if not in most, of the systems. While we cannot oer a specic, general model of
these exceptional ions, we provide a general introduction to the known properties of
such species. Furthermore, we argue that these species comprise the rule rather than the
exception. The reader is invited to reach his or her own conclusions.
2. ELECTRONS AND SOLVENT ANIONS IN SUPERCRITICAL CO
2
The rst exceptional system that we review is carbon dioxide [1521]. Supercritical (sc)
CO
2
nds numerous industrial applications as a green solvent, and this practical con-
sideration stimulates interest in its radiation chemistry. Though the studies of sc CO
2
are
recent, this system is particularly interesting because of the simplicity of the solvent
molecule and extensive gas phase and matrix isolation studies of the corresponding ions
(see below).
Like other sc uids, sc CO
2
is a collection of nanoscale molecular clusters that
rapidly associate, dissociate, and exchange molecules among each other [22]. Prethermal-
ized electrons in sc CO
2
attach to these (CO
2
)
n
clusters. In the gas phase, the attachment
can be dissociative [reaction (2)] and or nondissociative [reaction (1)],
e
CO
2

n
! CO
2

n
1
!COO
CO
2

n1
!COCO
3
CO
2

n2
2
depending on the electron energy [for n=2, reaction (2) is 3.6 eV more endothermic] [23].
Although in radiolysis, a large fraction of electrons have initial excess energies >10 eV, the
yield of CO
3
in 20 MeV electron radiolysis of dense sc CO

2
does not exceed 5% of the
total ionization yield [20].
In the gas phase, anions formed in reaction (1) have been extensively studied [24]. A
linear CO
2
molecule has negative gas-phase electron anity (EA
g
) of 0.6F0.2 eV. The
metastable C
2v
monomer anion, CO
2
(with OCO angle of 135j and autodetachment time

of <100 Asec) exhibits vertical detachment energy (VDE) of 1.331.4 eV. This energy
increases to 2.62.79 eV in the stable, D
2d
symmetric CC bound dimer anion, C
2
O
4
,
shown in Fig. 1a (with lifetime>2 msec), and further increases to 3.4 eV for n = 6 clusters.
In larger clusters, the VDE rst decreases to 2.49 eV (n = 7), then monotonically increases
to 3.14 eV (n = 13); then, for nz14, the VDE suddenly increases to 4.55 eV. The onset of
the photoelectron spectrum increases from 1.5 eV for n = 27 clusters to 1.82 eV for n =
813 clusters to 3 eV for n = 1516 clusters. Tsukuda et al. [24] argue that while the core
of small (nV6) and large (nz14) clusters is a D
2d
dimer anion, the core of 6<n<14 clusters
is a monomer anion weakly coupled to several CO
2
molecules (with binding energy ca.
0.22 eV per molecule). Both of these forms coexist in n = 6 and n = 13 clusters. It appears
that the two isomers are close in energy, and core switching readily occurs when the cluster
geometry and size change. Because in sc uid there is a wide distribution of the cluster sizes
and shapes [22], the solvent radical anion does not have a well-dened geometry.
In CO
2
gas, the density-normalized electron mobility l
e
s
e
is independent of temper-
ature (2 10
22
molecule/cm V sec [25]), although the apparent mobility steadily decreases
with the pressure: free electrons are trapped by neutral (CO
2
)
n
clusters (n
c
6) with nearly
collisional rates, and the electron anity of these clusters >0.9 eV. When extrapolated to
solvent densities of (215) 10
21
cm
3
typical for sc CO
2
, these estimates suggest that the
free electron mobility l
e
is ca. 1 cm
2
/V sec and its collision-limited lifetime s
e
<30 fsec [18].
If the lifetime were this short, the electrons would negligibly contribute either to the
conductivity or the product formation. However, this extrapolation is not supported by
experiment [18,20].
In low-temperature solid matrices (e.g., Ne and Ar at 511 K), the CO
2
monomer,
(CO
2
)(CO
2
)
n
multimer anion (n = 1, 2), and the C
2
O
4
dimer were observed using IR

spectroscopy; the latter species was the only one stable at 2531 K [26]. In nonpolar
liquids, monomer CO
2
is an ecient electron scavenger. Still, the electron can be detached
from the monomer anion both thermally and photolytically [27]. For instance, in iso-
octane, reaction (1) is exothermic by 1.08 eV, the VDE peak is at 3 eV, and the photo-
detachment threshold is at 1 eV [27].
As seen from above, the mode of electron trapping in sc CO
2
cannot be deduced
from the results obtained in the gas phase or matrix isolation studies. It is not obvious
whether the solvent radical anion should be similar to multimer cluster anions found in the
gas phase, dimer cation(s) in solid matrices, or monomer CO
2
anions in inert liquids. Such

a situation is typical for other molecular liquids.
Figure 1 (a) The structure of D
2d
symmetric (CO
2
)
2
dimer radical anion. (b) Visualization of

rapid resonant charge hopping in sc CO
2
. The hopping barrier is 0.46 eV; the residence time of the
charge on a given (dimer) molecule is 0.6 to 4 psec, depending on the solvent temperature [18]. (c)
Reduced density (q
r
) dependence of solvent anion mobility l () for four temperatures. The activation
energy does not depend on density; the mobility exponentially increases with the solvent density.
Time-resolved laser d.c. photoconductivity and pulse radiolysistransient (electro)-
absorbance studies of sc CO
2
showed that ionization of the solvent (or UV-light absorbing
solute) yields two negatively charged species: a metastable (quasifree) conduction band
(CB) electron and a rapidly hopping multimer anion (a self-trapped electron) [18,20]. Both
of these species exhibit unusual properties that account for many oddities observed in
radiolysis of sc CO
2
. Quasifree electrons in sc CO
2
have lifetime s
e
<200 psec and mobility
l
e
>100 cm
2
/V sec [18]. For reduced solvent density q
r
>1.2 (dened as the ratio of the
solvent density q and the critical density q
c
= 0.468 g/cm
3
), the product q
r
l
e
s
e
exponen-
tially increases with q
r
. The onset for the formation of rapidly migrating quasifree
electrons coincides with the emergence of the CB in the solvent [18]. Exactly the same
behavior was observed by Itoh et al. [28] for sc saturated hydrocarbons (see Chap. 8).
Their studies suggest that the electron mobility increases exponentially with density
between q
r
= 1 and 2 and then stabilizes and/or slightly decreases at greater density. In
sc CO
2
, the product l
e
s
e
shows signs of saturation at the reduced density of 1.8 (reaching
ca. 2.510
9
cm
2
/V) [18]. Both this behavior and the high mobility indicate that the
quasifree electron is not attached by CO
2
clusters, even temporarily, before it is nally
trapped. This is surprising, given the extremely rapid rate of electron attachment to (CO
2
)
n
clusters in the gas phase. Apparently, once the CB is formed in a dense liquid, the electron
dynamics dramatically changes.
In sc CO
2
, both the solvent viscosity and the mobility of solute ions (e.g., halide
anions and aromatic and alkylamine cations) are a function of the solvent density rather
than the solvent temperature and pressure separately [18,21]. In other words, if the density
is constant, the ion mobilities do not change with the solvent temperature. At a given
temperature, the ion mobility decreases rapidly with q
r
for 0.2<q
r
<1 and then decreases
slowly for 1<q
r
<2 [18,21]. In contrast to this behavior, the mobility of the solvent anion
exponentially increases with q
r
, being 210 times greater than the mobilities of all other
ions in sc CO
2
[18]. The activation energy of the solvent anion migration is 0.46 eV (for
constant q
r
) whereas for the solute ions (Fig. 1c), this energy is less than 20 meV [18,21].
Careful analysis of the data on the solvent anion and electron dynamics and thermochem-
istry indicate that an equilibrium between the quasifree and trapped electrons, similar to
that observed in saturated hydrocarbons (Chap. 8), cannot account for the observed
dynamics. This is reasonable, given that the trapping energy of the electron is almost an
order of magnitude larger in sc CO
2
than in these hydrocarbons.
Anomalously high mobility and large activation energy for migration of the solvent
anion suggests that this anion migrates by rapid charge hopping between the solvent
clusters (Fig. 1b); this hopping easily outruns Brownian diusion of the core anion [18].
The hopping mechanism is also suggested by the fact that the mobility exponentially
increases with q
r
, at any temperature: As the solvent density increases, the cluster-to-
cluster distance decreases, and the coupling integral becomes greater; the hopping rate
increases accordingly.
Electron photodetachment upon laser excitation of the solvent anion above 1.76 eV
was observed (Fig. 2a,c) [18]. The cross section of photodetachment linearly increases
between 1.76 and 3 eV (Fig. 2b). Under the same physical conditions, the photodetach-
ment and absorption spectra of the solvent anion are identical (Fig. 2b) [20], suggesting a
bound-to-CB transition; the quantum yield of the photodetachment is close to unity. The
photodetachment spectrum is similar to the photoelectron spectra of (CO
2
)
69
clusters
observed by Tsukuda et al. [24] in the gas phase; it is distinctly dierent from the electron
photodetachment spectra of CO
2
in hydrocarbon liquids [27]. This suggests that a CC

bound, D
2d
symmetric dimer anion constitutes the core of the solvent radical anion [18,19].
Figure 2 (a) When metastable quasifree electron, e
qf
(with mobility >10 cm
2
/V sec) is trapped by
dense sc CO
2
solvent, a high-mobility radical anion, (CO
2
)
n
, withl() of 10
2
cm
2
/Vsec is formed. The
binding energy of the electron is 1.61.8 eV; the electron can be detrapped by absorption of a photon
with energy >1.76 eV. (b) Electron photodetachment (empty symbols) and photoabsorption (lled
circles) spectra of solvent radical anion in sc CO
2
. The arrow points to the onset of the
photodetachment band. (c) Photoinduced electron detachment in sc CO
2
observed by dc photo-
conductivity. The initial (clipped) narrow peak is the prompt conductivity signal from free electrons;
the time prole of this signal follows the shape of the 248-nmexcitation laser pulse. The arrows indicate
the delay times at which a second (532 nm) laser pulse was red. The 532-nm photoexcitation detraps
the electrons that subsequently trap within the duration of the 532-nm laser pulse (sharp spikes).
Both the electrons and the solvent anions react with nonpolar electron acceptor
solutes with EA
g
>0.4 eV [18]. For oxygen (EA
g
of 0.4 eV), the electron transfer from the
solvent anion to the solute (which yields a stable CO
4
anion) is reversible (Fig. 3); the free

energy of the corresponding reaction is 0.42 eV. The rates of the electron attachment and
solvent anion scavenging correlate with each other and the EA
g
. On the other hand, the
correlation of these rate constants with the free energy (DGj) of the overall reaction
(expected from Marcus theory of electron transfer) is very poor [18]. The same pattern is
observed for high-mobility solvent cations in nonpolar liquids (Sec. 5). The reason for this
behavior is that while the overall DGj depends on what happens to the products (e.g.,
solute ions) after the electron transfer (structural relaxation, solvation, fragmentation, and
bonding to the solvent), the activation energy of the reaction depends only on the vertical
electron anity (ionization potential) of the solvent anion (cation) and the solute [18]. This
can be rationalized assuming that the scavenging reaction occurs by direct electron
transfer to (or from) the solute: If the solute needs reorganization to accept (donate)
the electron, the reaction does not occur and the solvent ion migrates away from the solute
molecule. In other words, because of the extremely fast charge hopping, the lifetime of the
collision complex is always shorter than the time needed for stabilization of the solute ion
by solvation and/or structural relaxation. No such anomalies are observed for (relatively
slow) electron transfer reactions that involve regular ions in the same nonpolar liquids, and
those do conform to the Marcus theory (although, to our knowledge, the inverted region
has never been observed in such reactions). For example, rate constants for charge-
transfer reactions of solvent holes in sc CO
2
with electron donors (CO, O
2
, N
2
O, and
dimethylaniline) systematically increase with the ionization potential of the solute [15,16].
These solvent holes are C
2h
symmetrical OO bound (CO
2
)
2
+
cations that exhibit a
prominent charge resonance band in the visible, which suggests strong coupling in the
dimer [15,16,19,20]. These solvent cations exhibit normal diusion properties and rate
constants of diusion-controlled electron transfer reactions [15,16,20]; no ultrafast charge
hopping is suggested by the data [20]. Such a situation is common: No known liquid or
solid yields both high-mobility anions and high-mobility cations. The likely reason is that
at least one of these species has a tendency to form strongly bound dimer radical ions that
cannot rapidly migrate by the hopping mechanism (see below).
In sc CO
2
, only solutes with EA
g
>2 eV exhibit diusion-controlled kinetics for
reaction with the solvent anion (which is consistent with the electron trapping energy
between 1.6 and 1.8 eV that was estimated from the photodetachment spectrum) [18]. For
q
r
>0.85, the scavenging radii of these diusion-controlled reactions systematically
decrease with the solvent density, q
r
[18]. Interestingly, in addition to the electron transfer
reactions, solvent anions in sc CO
2
form 1:1 and 1:2 complexes with polar molecules that
have large dipole moments, such as water, aliphatic alcohols, alkyl halides, and alkyl
nitriles [29]. None of these polar low-EA
g
solutes directly reacts with quasifree electrons in
sc CO
2
. The complexation rate is 1050% of the diusion-controlled rate, the equilibrium
constants of the 1:1 complexation range from 10 to 350 M
1
depending on the solute, the
reaction heat is 15 to 21 kJ/mol, and the reaction entropy is negative [29]. The stability
of these complexes increases with the dipole moment of the polar group and decreases with
substitution at the a-carbon. It appears that these complexes are bound by weak electro-
static interaction of the negative charge and the molecular dipole. Previously, such dipole-
bound complexes, with monomers of acetonitrile [30] and dimers and higher multimers of
aliphatic alcohols [31], were observed for solvated electrons in saturated hydrocarbons.
For these electrons, the complexation manifests itself through a precipitous decrease in the
electron mobility upon the addition of the solute: Thermal emission of trapped electrons
Figure 3 Reversible electron transfer reaction of the solvent radical anion in sc CO
2
with dioxygen.
The resulting O
2
anion rapidly forms OO bound complex with a solvent molecule, yielding a stable
radical anion, CO
4
. (a) The 532-nm photoexcitation can detach an electron from the solvent anion
(Fig. 1a). CO
4
is a 0.44 eV deeper trap and the electron cannot be detached from it. By determining
the magnitude of the spike from quasifree electrons (generated by 532-nm laser excitation of the
pholysate) as a function of time, one can obtain the decay kinetics of the solvent anion. (b) Ex-
perimental realization of this concept for a sc CO
2
solution containing 120 AM of O
2
. The conduc-
tivity signal (r) shown on the double-logarithmic scale shows a gradual transformation of the solvent
anion to CO
4
. The ratio Dr/r of the 532-nm laser induced conductivity signal to the conductivity
tracks the concentration of the solvent anion in a reaction mixture that contains both (CO
2
)
n
and
CO
4
. After the rst 10 Asec, this fraction persists at a small value; this represents the settling of the
equilibrium between the solvent anion and CO
4
.
from the complexes to the CB is much less ecient than that of free solvated electrons
(Chap. 8). No changes in the absorption band of the solvated electron in the NIR are
observed upon the complexation of these electrons with the monomers and dimers of polar
molecules [32]. Higher alcohol multimers, such as tetramers, provide very deep traps for
these electrons; absorption spectra of such cluster-trapped electrons are almost identical to
the spectra of solvated electrons in neat aliphatic alcohols [33].
That the solvent anion in sc CO
2
demonstrates behavior similar to that of solvated
electrons in saturated hydrocarbons suggests that the mechanism of binding to the polar
molecules must be similar. Apparently, increasing the trapping energy by ca. 0.15 eV
because of the electrostatic binding to a monomer or dimer molecule with a dipole
moment of (24) Debye is sucient to halt the charge hopping completely [29]. The same
eect of polar solutes on the hopping rate of high-mobility solvent radical cations (with
fairly similar thermochemistry) was observed in neat cis- and trans-decalin (Sec. 5).
sc CO
2
is not the only liquid for which high-mobility solvent anions are observed (see
below), but it is the simplest one. In monoatomic liquids (liqueed Ar, Kr, and Xe),
ammonia, and simple hydrocarbons (CH
4
, C
2
H
6
), solvent anions are not formed (quasi-
free or solvated electrons are formed instead; see Chap. 8). In diatomic liquids, such as N
2
and O
2
, solvent anions are generated, but the formation of strongly bound dimer anions
precludes rapid electron hopping. Even for CO
2
, high-mobility anions are not observed in
the low-temperature liquid: Considerable thermal activation is needed to break the dimer
anion prior to every hop of the electron. In liquids whose solute molecules show less
tendency to form strongly bound dimer anions, the electron hopping is faster and requires
much less activation energy. As argued below, such a situation occurs in carbon disulde,
hexauorobenzene, benzene, and toluene.
3. SOLVENT ANIONS IN LIQUID CS
2
, C
6
F
6
, AND AROMATIC
HYDROCARBONS
Carbon disulde is isovalent to carbon dioxide and it also has a bent monomer anion.
While gas-phase CO
2
has negative EA
g
of 0.6 eV [24], for CS
2
, EA
g
is +0.8 eV [34].
Despite this very dierent electron anity, Gee and Freeman [34] observed long-lived
electrons in CS
2
(with lifetime>500 Asec) with mobility ca. 8 times greater than that of
solvent cations. Over time, these electrons converted to secondary anions whose
mobility was within 30% of the cation mobility. Between 163 and 500 K, the two ion
mobilities scaled linearly with the solvent viscosity, as would be expected for regular ions.
Of course, Gee and Freemans identication of the long-lived high-mobility solvent anions
as electron is just a manner of speech: Obviously, quasifree or solvated electrons cannot
survive for over a millisecond in a positive-EA
g
liquid.
To the best of our knowledge, pulse radiolysistransient absorption studies of neat
CS
2
have not been reported. CS
2
anion in 0.1 M cyclohexane and 0.1 M THF solutions

appears as a single 275-nm peak [35]; there is no charge-resonance band that can be
attributed to the dimer anion, at early (<10 nsec) or later times.
The studies carried out in the gas phase and low-temperature matrices suggest that
(CS
2
)
n
anions have somewhat dierent structure from the (CO

2
)
n
anions discussed in the

previous section [24]. Similar to the (CO
2
)
n
anions, the CS
2
monomer and CC bound

C
2
S
4
dimer anions switch as the core of the (CS

2
)
n
anion [36]. However, unlike the two

core anions in the (CO
2
)
n
anions, CS
2
and C
2
S
4
anions coexist in the clusters of all sizes

(n=26) with the monomer core being statistically prevalent [36]. The dimer core is
responsible for the 1.51.8 eV peak observed in the photodestruction spectra of n=24
anions; no matching peak is observed in the liquid [37]. The dimer anion has either D
2h
(C
C bound) or C
2v
symmetry (CC and SS bound) rather than the D
2d
symmetry of the C
C bound C
2
O
4
anion [3638]. It is almost certain that the SS bound structure is

energetically preferable, because the UVVis photoexcitation of C
2
S
4
(CS
2
)
n2
anions
results in the fragmentation of the dimer core to C
2
S
2
and S
2
[37]. The dimer anion was
also observed in the EPR spectra of g-irradiated CS
2
-doped frozen alcohols; the g-tensor
parameters suggested SS bonding [39]. Interestingly, while C
2
O
4
is readily observed using

IR spectroscopy when electrons are injected in frozen CO
2
/Ne or CO
2
/Ar mixtures at 4 K
[26], only CS
2
is observed in similar mixtures doped with CS

2
[40]. It seems that
dimerization of the molecular anion in CS
2
is less favored than in CO
2
, both in the gas
and solid phaseperhaps because of the positive electron anity of the monomer
molecule.
Despite these structural dierences, both liquid CS
2
and sc CO
2
yield high-mobility
solvent anions whose mobilities are similar. The most striking dierence is the activation
energy for the anion migration. For CS
2
, this activation energy is only 5 kJ/mol [34]
whereas for CO
2
it is 46 kJ/mol [18]. Such a large dierence is surprising because similar
transport mechanisms were suggested for both of these anions. This result becomes more
understandable when other examples of high-mobility anions are examined.
A relatively long-lived (>100 nsec) high-mobility solvent anion has been observed by
microwave conductivity in room-temperature h-irradiated liquid hexauorobenzene
(C
6
F
6
) [41]. Like CS
2
, hexauorobenzene has positive EA
g
estimated to be between 1
and 2 eV [41]. The anion mobility is 40 times greater than that of the solute ions and the
activation energy for the solvent anion migration is 11 kJ/mol [41]. The electron in the sol-
vent anion is strongly bound: The anion does not react with such ecient electron acceptors
as SF
6
, although it reacts with CBr
4
, CCl
4
, and (NC)
2
C=C(CN)
2
(with rate constant as
large as 1.5 10
11
M
1
sec
1
). Addition of small amounts of inert solvents (benzene,
saturated hydrocarbons, C
6
F
12
) results in the exponential decrease in the anion mobility
with the molar fraction x of the inert solvent [41,42]. For example, addition of 5 mol% of
cyclohexane drops the mobility by 50% relative to neat C
6
F
6
[41]. This decrease can be
approximated by (1x)
n
, where the exponent n=1520. A percolation model of charge
migration [42] suggests that the negative charge in C
6
F
6
is spread over ca. 12 solvent
molecules; this is why even slight dilution has strong eect. The multimerization is also
consistent with the emergence of a 675 nm anion band (with molar extinction coecient of
5000 M
1
cm
1
) in pulse radiolysis of neat C
6
F
6
[41]. This band is dierent from the C
6
F
6
band observed in dilute solutions of C

6
F
6
in inert liquids; the latter is centered at 480 nm
[41]. Thermochemistry considerations suggest that the 675-nm band cannot be from a
sandwich dimer anion similar to the dimer cations of benzene and other planar aromatic
hydrocarbons [43]. This conclusion is consistent with optically detected magnetic resonance
(ODMR) and magnetic level-crossing data that indicate that in cold hydrocarbon sol-
utions, the encounter of C
6
F
6
with C
6
F
6
results in diusion-controlled degenerate electron
transfer rather than anion dimerization [44]. Thus, while the data clearly point to charge
sharing and charge hopping, there seems to be no evidence that a metastable dimer is
formed. Once more, one needs to postulate a exible-structure multimer anion in which
fractional negative charge freely exchanges between the solvent molecules.
Importantly, both for liquid C
6
F
6
and CS
2
, there is a relatively high yield of ortho-
positronium (o-Ps) observed in e
+
irradiation of these uids [34]. The o-Ps is formed in the
e
+
e
recombinations that occur in the end-of-track spurs. The higher the negative charge
mobility, the higher the probability that these e
+
e
recombinations occur before the e

+
undergoes pick-o annihilation with an electron bound in a solvent molecule. Following
Gee and Freeman [34], we suggest that high o-Ps yield is a general indicator for the
presence of high-mobility solvent anions in molecular uids with positive EA
g
.
Yet another example of a high-mobility anion is given by benzene and toluene [45],
whose molecules have negative EA
g
of 1 eV (see also Chap. 8, Sec. 4.6) In dilute solutions
of benzene and toluene in saturated hydrocarbons and tetramethylsilane, there is an
equilibrium between the solvated electrons and benzene/toluene anions [45]. This equili-
brium is shifted toward the anion (DGj of 9 kJ/mol), and this shift becomes greater at
higher pressure. At low pressure, the data for neat liquid benzene and toluene can be
interpreted the same way. However, at high pressure (12 kbar), the negative charge
mobility becomes independent of pressure, which indicates that no volume change occurs
during the charge migration [45]. Any mechanism that requires thermal emission of the
electron from the bound state back into the CB would require such a change; only resonant
charge transfer can account for the zero reaction volume. That the electron in pressurized
benzene is not quasifree also follows from the extrapolation of medium-pressure equili-
briumconstants to the high-pressure range. These estimates give an equilibriumconstant of
10100 for the bound electron. Simple calculation shows that the estimated fraction of free
electrons is too small to account for the observed negative charge mobility. Interestingly,
the activation energy for anion hopping in liquid benzene and toluene (0.12 and 0.13 eV,
respectively [45]) is very close to that in hexauorobenzene (0.11 eV [41]), despite a large
dierence in their EA
g
; the corresponding anion mobilities are also comparable. Liquid
benzene and toluene provide the only known examples of a pressure-induced switch from
the thermally activated electron detrapping to charge hopping.
As in the case of hexauorobenzene solvent anion, EPR and ODMR spectroscopies
suggests that no dimerization of monomer radical anions of benzene and toluene occur in
liquid benzene and/or in alkane solutions of benzene (whereas the radical cation of
benzene is known to dimerize rapidly). The conductivity studies also indicate that there is
no volume change associated with the dimerization [45].
We conclude this section with the following observations:
First, high-mobility anions occur both in liquids whose molecules have negative and
positive EA
g
. The gas-phase electron anity has no eect on the rate and the
activation barrier of electron hopping in neat liquid solvents.
Second, the formation of strongly bound dimer anions is detrimental for rapid
charge hopping. Indeed, the dimer must dissociate every time the negative
charge moves; this requires thermal activation. As discussed in Sec. 2, high-
mobility anions in sc CO
2
have dimer radical anions as their chromophore
core; this only results in a higher activation barrier for hopping and a moderate
increase in the anion mobility relative to that of solute ions (a factor of 2 at the
critical temperature). By contrast, high-mobility solvent anions in liquid CS
2
,
hexauorobenzene, benzene, and toluene (for which the tendency for anion
dimerization is weak), have 35 times lower activation barriers for the charge
hopping and substantially higher migration rates (up to 15 times) than the
solute ions. We speculate that the only reason why high-mobility solvent
anions are observed in sc CO
2
at all is the fact that the core rapidly switches
between the monomer and dimer anion with change in the cluster size.
Third, charge delocalization over many solvent molecules, perhaps as many as 1015,
seems to be the only way to explain the observations (such as the eect of the
dilution on the conductivity and the emergence of new absorption bands in the
UVVis spectra). Classifying these solvent anions as molecular ions solvated by
their parent liquids or solvated electrons does not explain these properties.
It may appear from the above that only nonpolar liquids yield nonmolecular
solvent anions upon the ionization. Perhaps this is misleading: Most polar liquids studied
by radiation chemists are aliphatic alcohols and water, and these liquids yield solvated
electrons rather than radical ions. Although there has been sporadic interest in other polar
liquids (e.g., neat acetone), the current state of knowledge of such systems does not allow
one to reach any conclusion as to the nature of the reducing species observed therein
(although, see Sec. 4).
It may also appear that the few nonpolar liquids considered above do not comprise
the rule. Again, we stress that the most extensively studied nonpolar polyatomic liquids
are saturated hydrocarbons; it so happens that these uids also yield solvated electrons
(that are in a dynamic equilibrium with quasifree CB electrons). Actually, very few
nonpolar liquids other than alkanes and liqueed rare gases have been studied by pulse
radiolysis or photoconductivity. In almost all such systems, either the hole or the
electron exhibits unusual migration or reaction dynamics that are suggestive of rapid
charge hopping. Given that in many liquids, the primary solvent ions are short-lived, we
hazard a conjecture that most liquids that do not yield solvated electrons yield high-
mobility, multimer solvent anions or (as shown in Sec. 5) solvent holes. The true scope for
the occurrence of such ions is not known, but the number of examples steadily increases.
4. SOLVENT ANIONS AND ELECTRON LOCALIZATION IN LIQUID
ACETONITRILE
The previous examples of high-mobility solvent radical anions were all in nonpolar liquids.
What happens in polar liquids? In some polar liquids (whose molecules have negative EA
g
)
such as water, mono- and poly-atomic alcohols, and ethers, solvated electron is observed
(Chaps. 7 and 8). In this species, the excess electron density is mainly outside the solvent
molecules. The electron resides at the cavity center and interacts as a point-like negative
charge with the surrounding solvent dipoles. The greater the dipole, the more stable is
the solvated electron. A link between these energetics and the solvent polarity is observed
in the bell-like visible or near-infrared (NIR) spectra of the solvated electrons [1]. The
maximum of the band systematically shifts toward the blue as the polarity of the solvent
increases. For obvious reasons, these solvated electrons are not observed in liquids whose
molecules have positive EA
g
. However, there is no a priori reason to believe that a given
negative-EA
g
polar liquid will yield solvated electrons upon ionization. Even if the
monomer has negative EA
g
, the dimer may have positive electron anity, especially in
a liquid solution where the electrostatic eld of the solvent (considered as a polarizable
dielectric continuum) can stabilize the corresponding dimer anion. For hydroxylated mo-
lecules, such as water and aliphatic alcohols, stabilization via the formation of a dimer (or
multimer) anion is lacking, because no low-lying unoccupied molecular orbitals (MOs) are
readily accessible for the excess electron. By contrast, many organic molecules have readily
accessible C and N 2p orbitals in their lowest unoccupied molecular orbitals (LUMOs);
these are the atomic orbitals involved in the formation of CC bound dimer anions in CO
2
and CS
2
considered in Secs. 2 and 3, respectively.
Below, we consider a polar, negative-EA
g
liquidacetonitrilein which the dimer
anion formation (because of the electron accessing low-lying k* orbitals) competes with
electron stabilization because of the formation of a polarized solvent cavity [30,46]. The
outcome of this competition depends on the solvent temperature, as the dimer anion is in a
dynamic equilibrium with a more energetic cavity electron. The latter cannot be regarded
as solvated electron because the partition between the valence electrons in the solvent
molecules and the excess electron at the cavity center is incomplete [30]. We argue that the
properties of these two electron states can only be understood when the traditional one-
electron approximation is abandoned in favor of many-electron model.
Like water and aliphatic alcohols, gas-phase CH
3
CN monomer has a large dipole
moment (4.3 D) and negative vertical EA
g
of 2.84 eV (adiabatic EA
g
is +17 meV) [47].
CH
3
CN
is a classical example of a dipole-bound anion, with the electron in a diuse

orbital (> 3 nm) [47]. While neutral dimers in which the CH
3
CN dipoles are coupled in an
antiparallel fashion readily form in vapor and in liquid [48], the dimer anion, {CH
3
CN}
2
,
has not been observed in the gas phase. In the neutral trimer, one of the monomers couples
sideways to the antiparallel pair; this molecule binds the electron in the same way as the
monomer; the adiabatic electron anity of this trimer (1420 meV) is higher than that of
the monomer [47]. Higher multimer anions, {CH
3
CN}
n
, were found only for n>12 [49].

The stabilization of excess electron in solid and liquid acetonitrile is a concerted eect of
many solvent molecules. One would expect that the electron in solid and liquid acetonitrile
localizes in the same way as the solvated/trapped electron in water and alcohols. This
expectation is not borne out.
Solid acetonitrile exists in two crystalline forms, a high-temperature phase, a, and a
low-temperature phase, h [50]. When ionized at 77 K, a-acetonitrile yields a dimer radical
anion, while h-acetonitrile yields a monomer radical anion [51]. The observed dichotomy
follows from the crystal structure: In a-acetonitrile, the dimer anion retains the same
reection plane and inversion center as the symmetric antiparallel pair of CH
3
CN
molecules [52]. h-acetonitrile consists of innite chains of parallel dipoles (no antiparallel
pairs are present) and a monomer anion is formed instead [51,52]. Electron paramagnetic
resonance experiments and ab initio calculations of Williams et al. [51] indicate that the
dimer radical anion is C
2h
symmetrical and has the staggered, side-by-side structure shown
in Fig. 4a [46,52]. The mechanism for orbital stabilization of bent acetonitrile molecules in
the dimer is illustrated in Fig. 4b. The CCN angle is 130j and the distance between cyanide
carbons is 0.165 nm. The negative charge and spin are mainly on carbonyl N and methyl C
atoms. This structure accounts for the observed EPR parameters and vibronic progres-
sions observed in the charge-resonance band of the dimer radical anion [51,52]. The
monomer radical anion in h-acetonitrile is also bent; the CCN angle is close to 131j [52].
In both of these anions, the CC bond is stretched to 0.153 nm (vs. 0.1443 nm in neutral
CH
3
CN). Photoexcitation of these radical anions (<650 nm) causes further elongation of
the NCCH
3
bonds (because of the promotion of electron into the corresponding CC
antibonding orbital), which leads to their fragmentation to CH
3
and CN
(see Fig. 4b).

Except for the vibronic progressions, both radical anions exhibit similar absorption
spectra in the visible (see Fig. 3 in Ref. 51). For the dimer radical anion, the absorption
band is centered at 530 nm, for the monomer radical anion at 420 nm [51]. The positions of
these bands are in good agreement with ab initio calculations [52]. These calculations
indicate that no bound-to-bound transitions in the IR are possible, either for the monomer
or the dimer radical anion [46,52].
In liquid acetonitrile, there are two radical anions present shortly after the ionization
event: anion-1 that absorbs in the NIR (whose band is centered at 1.45 Am) and anion-2
that absorbs in the 400800 nm region (whose band is centered at 500 nm); see Fig. 5a
[46,53]. These two anions are in a rapid dynamic equilibrium (Fig. 5b): As the liquid is
cooled, the 1.45-Am band becomes more prominent and the 500-nm band less prominent
[53]. From the temperature dependencies of the transient absorption spectra, it was
estimated that anion-2 is 0.36 eV more stable than anion-1 [53]. The transformation of
anion-1 to anion-2 is rapid at room temperature [40,46,53] but fairly slow at the lower
temperature; at 30jC, it takes 2050 nsec [53].
While it was initially suggested that anion-1 and anion-2 are the monomer and the
dimer radical anions of acetonitrile [53], respectively, more recent work suggests that
anion-1 cannot be a monomer anion (which in any case has a dierent absorption
Figure 4 (a) Singly occupied molecular orbital (SOMO) of dimer radical anion of acetonitrile
(from a density functional calculation); (b) a scheme for the formation of the SOMO and the doubly
occupied subjacent orbital from k and k* orbitals of neutral acetonitrile molecules.
spectrum from anion-1, as explained above) [30,46]. Actually, the absorption spectrum of
anion-1 is very similar to that of solvated electron in saturated hydrocarbons. This is
understandable because the CN dipole has negative charge on the nitrogen. Consequently,
if a cavity electron were formed in acetonitrile, this cavity would be lined by methyl rather
than CN groups [30]; that is, the rst solvation shell of the s electron would resemble that
of the solvated/trapped electron in liquid and vitreous alkanes.
The NIR location of the absorption band for a hypothetical cavity electron in
acetonitrile makes even more sense if one recalls that there is a linear correlation between
the position of the band maximum of a cavity electron in a given polar liquid and the
position of the CTTS band maximum for a given halide anion in the same liquid [46,54].
Figure 5 (a) Typical end-of-pulse absorption spectra obtained in pulse radiolysis of room tem-
perature liquid acetonitrile (7-nsec fwhm pulse of 20 MeV electrons). The 500-nm peak is from
anion-2 (dimer radical anion); the 1450-nm peak is from anion-1 (cavity electron). (b) Energy dia-
gram and sketches of anion-1 and anion-2 (see the text).
The absorption band of anion-1 perfectly ts on this correlation plot (predicted 1.48 Am
[54] vs. the observed 1.401.45 Am [46]).
Not only does anion-1 dier from the molecular anions of acetonitrile in its
absorption properties, but its dynamic properties are also anomalous. While anion-2
has normal mobility, anion-1 is a high-mobility anion whose room temperature diusion
coecient is more than three times higher than that of solute ions and anion-2 [30]. The
activation energy for this migration is just 3.2 kJ/mol while the value for normal ions
(including anion-2) is 7.6 kJ/mol [30]. Electron-transfer reactions that involve anion-1
proceed with rate constants approaching 10
11
M
1
sec
1
[30,46]. These reactions can be
directly observed on a subnanosecond time scale (before the equilibration of the two
anions) using ultrafast pump-probe laser spectroscopy. To this end, Kohler et al. injected
the electron into room temperature liquid acetonitrile using one-photon CTTS excitation
of iodide [46]. Both anion-1 and anion-2 were observed within 300 fsec after the excitation
with a 200-fsec, 260-nm pulse, and rapid decay of anion-1 in the presence of CHCl
3
was
observed [46]. The same experiment gave an estimate of 0.26 nsec for the settling of the
equilibrium between the two anions.
In the time-resolved photoconductivity experiments carried out at Argonne [30], the
anion equilibrium was observed via non-Arrhenius temperature dependencies of anion
mobility and rate constants of scavenging by electron acceptors, such as CCl
4
[30]. These
conductivity experiments clearly demonstrate that the high-mobility anion is anion-1
rather than anion-2, contrary to previous suggestions [55]. To distinguish between the
two anions, anion-1 and anion-2 were photoexcited in their respective absorption bands
using 1064 and 532 nm, 6-nsec laser pulses; this photoexcitation causes anion fragmen-
tation to CH
3
and CN (with quantum yields of 0.01 and 0.32, respectively) and a decrease
in the d.c. conductivity. Using 532 nm photobleaching of anion-2, the equilibrium fraction
of this anion between 20jC and 50jC was determined; knowing this fraction, the mo-
bility and reaction constant for each anion were determined and the equilibrium constant
(1.3 at 25jC) and the heat of anion conversion (which is ca. 0.46 eV) were estimated. The
photon uence dependencies of the photobleaching eciency gave estimates for the an-
ion conversion rate. These measurements suggested a longer time constant of 3 nsec
(vs. 0.26 nsec obtained in Ref. 46) for settling the equilibrium between the two anions at
25jC.
The formation of CH
3
CN
in solid h-acetonitrile is a result of its favorable crystal

structure [50]. According to x-ray diraction and nuclear magnetic resonance (NMR)
data, the short-range structure of liquid acetonitrile is similar to that of crystalline a-
acetonitrile, with a pentamer as the basic unit [56]. The prevalent orientation of the ace-
tonitrile molecules in the liquid is the antiparallel pair of the type found in a-acetonitrile.
Given that dimerization strongly reduces the energy of the anion [46,51,52], it seems likely
that the monomer anion cannot form in liquid acetonitrile, where the special arrange-
ment of neighboring molecules needed for the formation of the monomer anion is not
possible.
While anion-2 is clearly the dimer radical anion of acetonitrile, identication of
anion-1 as a cavity electron requires caution. First, we stress that anion-1 cannot be the
monomer anion of acetonitrile. The monomer anion does not absorb in the NIR
[30,46,52]. For the monomer anion to occur at all, the neighboring acetonitrile molecules
should all be oriented in the same direction, as in h-acetonitrile; otherwise, coupling to a
neighboring (antiparallel) molecule reduces the overall energy and causes instant dimer
formation. It is dicult to see how such a fortuitous orientation could persist for 0.33
nsec in a room temperature liquid. Also, it is not clear why a monomer anion would
rapidly migrate. The only migration mechanism possible for this anion would be charge
hopping. Assuming that this hopping is between neighboring molecules (separated by 0.4
nm) and the diusion coecient is 8.3 10
4
cm
2
/sec (estimated from the room-tem-
perature mobility of 3.3 10
4
cm
2
/V sec [30]), the residence time for the charge on a
given molecule is 2 psec. This implies that 10
2
10
3
hops occur prior to the transformation
of the monomer anion-1 to anion-2. The lowest bending modes of the CCN fragment of
acetonitrile molecules and anions are 300330 cm
1
, which is equivalent to 0.1 psec in time
units. Thus although the diusion is fast, the lifetime of a given monomer anion is
suciently long for the structural relaxation; in other words, this monomer anion must be
a bent species like CH
3
CN
in h-acetonitrile. Thus the low-barrier resonant charge trans-

fer needed to explain the high mobility would have to be between a strongly bent anion
and a linear neutral molecule. Such a process cannot proceed with a low activation energy
because bending of the neutral molecule and solvation of the resulting anion require much
energy. Furthermore, never once in a series of these 10
2
10
3
hops could the two molecules
involved in the resonant charge transfer be in the antiparallel orientation, because then
anion-1 would couple to the neighboring molecule yielding anion-2. It appears that the
monomer anion cannot account for any property of anion-1.
It is more likely that the high-mobility anion-1 is a multimer anion in which the
charge is spread over several acetonitrile molecules, like the analogous species in nonpolar
liquids that were examined in Sec. 3. Because of the reduction in the charge on the
individual molecules, their bending is less strenuous and the barrier for the migration of
the multimer anion is low. Such a multimer anion is actually no dierent from the solvated
electron in alkanes (see below), which accounts for the striking similarity between the
absorption spectra of anion-1 and solvated/trapped electrons in saturated hydrocarbons.
We suggest that acetonitrile provides a rare example of a liquid in which the solvated
electron (multimer anion) coexists with a moleculardimerradical anion.
To investigate possible structures of the multimer anion, a {CH
3
CN}
3
cluster was
modeled using a density functional (B3LYP) method [30]. A 631+G** basis set that
included polarized (d,f) and diuse functions was used and the C
3h
symmetry was imposed.
A ghost hydrogen atom with zero charge was placed at the center of the cluster to
provide s-functions for the solvated electron. The polarizable (overlapping spheres)
continuum model was implemented in the integral equation formalism. The lowest energy
state was a propeller-like 2AV state shown in Fig. 6. The CCN angle in the acetonitrile
subunits is 178j in vacuum and 168j in solution (vs. 180j in the neutral molecule). This
bending is considerably smaller than in the monomer and dimer anions (ca. 130j). The
solvated cluster anion is compact: The closest methyl hydrogens are 0.171 nm away from
the symmetry center. The CC bond in the acetonitrile subunits is elongated from 0.144 to
0.148 nm, while the CN bond is very slightly changed. In this structure, the singly
occupied molecular orbital (SOMO) envelopes the whole cluster anion. The main negative
nodes are on methyl carbons, while the main positive nodes are at the center of symmetry,
on the in-plane hydrogens, and on carbonyl carbons. This structure may be viewed both
as a multimer anion and a solvated electron: The SOMO has a noticeable s-character at
the symmetry center (ca. 0.34), although the main spin density is on the methyl carbons.
The latter atoms exhibit large hyperne coupling constants (hfcc) for
13
C: the isotropic
hfcc is 6.9 mT; the anisotropy is negligible. Isotropic hfcc for methyl protons are relatively
small: 0.19 mT for in-plain hydrogens (the principal values of the dipole tensor are 0.29,
0.15, and 0.44 mT) and 0.086 mT for out-of-plane hydrogens (0.29, 0.16, and
+0.45 mT, respectively). The isotropic hfcc for cyanide
13
C and
14
N nuclei are 0.4 and
0.36 mT, respectively.
The structure bears strong resemblance to the trapped electron in saturated hydro-
carbons studied by Kevan et al. [2]. The electron is solvated by methyl groups; the
positive charge on these groups is increased because of the considerable elongation of CC
bonds. This elongation, as demonstrated by our discrete Fourier transform (DFT)
calculations, is the consequence of large electron density on the skeletal carbon atoms.
In the semicontinuum model of Kevan et al. [2], this (multielectron) interaction is treated
in terms of a polarizable CC bond; our calculation justies their ad hoc approach. The
Figure 6 Singly occupied molecular orbital (SOMO) of a propeller-like trimer radical anion of
acetonitrile obtained using density functional theory. The structure was immersed in a polarizable
dielectric continuum with the properties of liquid acetonitrile. Several surfaces (on the right) and
midplane cuts (on the left) are shown. The SOMO has a diuse halo that envelops the whole cluster;
within this halo, there is a more compact kernel that has nodes at the cavity center and on the
molecules.
size of the solvation cage, the juxtaposition of methyl groups, and the hfcc tensors for
methyl protons favorably compare with those experimentally obtained by Kevan et al. for
the trapped electron in frozen 3-methylpentane [2]. Therefore it is reasonable that the
multimer {CH
3
CN}
n
anion absorbs much like the solvated/trapped electron in alkanes.

While a rst-principle calculation for a larger cluster is impractical, it is possible to
make an educated guess as to what happens to the anion when the cluster size increases.
The propeller structure obtained for the {CH
3
CN}
3
anion is similar (save for the

elongated CC bonds) to that of the {CH
3
CN}
n
X
(X=I, Br) cluster for n = 3 [57]. One

may expect that this trend will pertain to larger size clusters. When the halide anion is
solvated by less than seven acetonitrile molecules, the core anion is a star structure with
radial CH
3
CN dipoles looking away from the halide anion [57]. For n>912, the
molecules in the rst solvation shell couple in an antiparallel fashion to the molecules in
the second solvation shell, so that some molecules in the rst solvation shell are oriented
tangentially rather than radially [57]. Perhaps, small {CH
3
CN}
n
anions (nV6) are also

star-shaped. Because of the further spread of the electron density in such clusters, the s-
character of the SOMO increases while the CCN bending and CC bond elongation
decreases: Such an anion would be more like a solvated electron.
To conclude this section, acetonitrile is an example of a polar liquid in which
stabilization of the excess electron via the formation of a dimer anion is energetically
favored over the formation of a cavity electron, despite the fact that the molecule has one
of the largest dipole moments and very negative EA
g
. The cavity electron still occurs in
this liquid as a metastable state at the high temperature. This state cannot be truly
regarded as solvated electron because the electron density is shared both by the solvent
molecules and interstitial sites; the excess electron is not separable from the valence
electrons of the solvent. A similar situation exists for trapped electrons in vitreous
hydrocarbons. These species should be regarded as multimer anions with exible geometry
and extensive delocalization of the charge. These solvated electrons are just variants of
multimer radical anions that occur in many liquids, both polar and nonpolar, including
the several examples examined above.
5. SOLVENT RADICAL CATIONS IN LIQUID CYCLOALKANES
At rst glance, it may appear that extensive delocalization and/or rapid charge hopping
should not occur for solvent radical cations because the valence hole is more strongly
associated with the molecule than the excess electron. We have already seen that such
expectations are not supported for solvent anions, were the delocalization and degenerate
electron exchange occur for liquid solvents whose molecules dier by more than 2 eV in
their electron anity. The same applies to the solvent holes: The fact that a given molecule
forms a well-dened radical cation when this molecule is isolated in an inert matrix does
not mean that the same species is formed in a liquid where all molecules are alike. The last
few examples discussed in this chapter are high-mobility solvent holes in cycloalkanes:
cyclohexane, methylcyclohexane, and decahydronaphthalenes (decalins) [58,59,60].
We forewarn the reader that the formation of high-mobility holes is not peculiar to
these four cycloalkanes: For instance, cyclooctane [61], squalane [62,63,64], and CCl
4
[65]
also yield such holes. However, in these other liquids, the holes are unstable and,
consequently, more dicult to study (the lifetimes are 520 nsec vs. 13 Asec). This
explains why convincing demonstrations for the occurrence of high-mobility holes are
slow to come. For example, squalane (by virtue of its high viscosity) has been frequently
used in the studies on uorescence and magnetic and spin eects in pulse radiolysis.
Despite these many studies, it has only recently been recognized that its short-lived hole
(with lifetime <20 nsec) has abnormally high diusion and reaction rates [62]. Shortly
after this fact was established using transient absorption spectroscopy, subsequent studies
conrmed the hopping mechanism, as fast diusion with degenerate electron exchange and
high-rate scavenging reactions of the squalane holes were observed using time-resolved
ODMR [62], magnetic level-crossing, and quantum beat spectroscopies [63]. Rapid
scavenging reactions of the squalane hole were also found to account for the anomalies
in the magnetic eld eect observed for delayed uorescence in the VUV excitation of
squalane [64]. Basically, in such systems, one needs to know where to look; once the
property is established, it can be demonstrated in several ways, using dierent techniques.
In cyclooctane, high-mobility solvent holes were observed using time-dependent
electric-eld-modulated delayed uorescence [61] and by observation of rapid scavenging
of cyclooctane holes by aromatic solutes in the initial stage of radiolysis. Recently, there
has been a suggestion of the presence of such holes in cyclopentane and cycloheptane [61];
their natural lifetimes must be <5 nsec. Faster-than-normal scavenging of short-lived
isooctane holes by diphenylsulde and biphenyl was observed using quantum beat and
transient absorption spectroscopies [66]. A controversy exists as to the presence of high-
mobility holes in liquid CCl
4
[65].
These disparate ndings hint that there may be many examples of rapidly migrating
(delocalized) solvent holes in molecular uids: The known systems are few because it is
dicult to establish these properties for short-lived species. As the time resolution
improves, more examples might follow. In most saturated hydrocarbons, fragmentation
and proton transfer limit the lifetime of the solvent hole to several nanoseconds (or less)
[58] and, therefore, little is known about their dynamics. On the other hand, the most
studied alkane liquids, parans, do not seem to yield high-mobility solvent cations [67].
This is because many conformers coexist in these liquids, some of which have higher
ionization potential than others. Variations in the binding energy of the hole stall its rapid
hopping because thermal activation is needed to detrap the hole from the low-IP
conformers. That conformation dynamics and isomerism play an important role in the
charge hopping is supported by many observations (note, e.g., that high-mobility solvent
anions are known to occur only in liquids whose molecules are rigid). As for the parans,
while no rapid hole hopping is observed in liquid alkanes, in low-temperature crystals
(where all molecules have the same extended conformation) this exchange is very fast and
can be readily observed by means of time-resolved and/or cw ODMR [68]. Ironically, in
these n-alkane crystals, the hole migrates much faster than the hole in frozen cycloalkanes,
because the latter solids exhibit more structural disorder (because of the formation of
plastic crystal and glass phases) detrimental to hole hopping; thus the situation is exactly
opposite to that in a liquid. The recent magnetic level-crossing spectroscopy study of
Borovkov et al. places an upper estimate of just 10
8
M
1
sec
1
for degenerate electron
exchange between n-nonane
+
and the parent alkane molecule in room temperature
solution [68].
The reader may notice that only saturated hydrocarbons (with a possible exception
of CCl
4
) have been observed to yield rapidly migrating solvent holes. As mentioned above,
part of this bias is explained by the fact that the holes are usually short-lived, so their
dynamic properties are dicult to study. However, in many liquids (such as aromatic
hydrocarbons and sc CO
2
), the solvent holes are relatively stable, yet no rapid hole
hopping is observed. In such liquids, the solvent hole has a well-dened dimer cation core
with strong binding between the two halves (in the rst place, it is this dimerization that
causes the hole stability). For example, solvent holes in aromatic liquids are sandwich
dimer cations with overlapping k systems [43]; in sc CO
2
, the solvent cation is an OO
bound molecular dimer [19], etc. This strong dimerization is detrimental to charge
delocalization and rapid hopping. High temperature is needed to overcome this hindrance;
perhaps high-mobility holes more readily occur in hot (e.g., supercritical) liquids. In many
room temperature liquids, a catch-22 situation occurs: For the solvent radical cations to be
stable toward fragmentation and proton transfer, these holes must dimerize. The dimer
radical cations are long lived and can readily be studied; however, they have ordinary
dynamic properties. The holes that do not dimerize might have interesting dynamic
properties but they are unstable and, therefore, dicult to study. As a result, one is limited
to the studies of the few solvent holes that do not dimerize and yet are long-lived.
In cycloalkanes, proton transfer is weakly endothermic, conformational dynamics is
slow, dimerization is not favored, and the high-mobility solvent holes can be readily
observed [60]. Ionization of cyclohexane, methylcyclohexane, trans-decalin, and cis-decalin
produces cations whose mobilities are 5 to 25 times greater than the mobilities of normally
diusing molecular ions and (in some cases) thermalized electrons in these liquids [58,59,60].
Long lifetime and high mobility makes it possible to study the reactions of these holes using
time-resolved microwave and d.c. conductivity, an option that does not exist for other
saturated hydrocarbons. The activation energies for the hole mobility range from (3F1)
kJ/mol for trans-decalin and cyclohexane to +(78) kJ/mol for methylcyclohexane and cis-
decalin [58]. Methylcyclohexane has the largest temperature interval where it is liquid at
atmospheric pressure and exhibits a single activation energy of hopping (7.8 kJ/mol)
between 133 and 360 K [69]. The activation energies for the highest-rate scavenging re-
actions of the cycloalkane holes range from 4 to 9 kJ/mol [58]. All these activation energies
are small, suggesting low barrier for resonant charge transfer.
Dynamic and chemical properties of the cycloalkane holes have been reviewed
[58,59], and we refer the reader to these publications for more detail. Below, we briey
summarize the main ndings. Although the cycloalkane holes are paramagnetic species,
these holes cannot be observed by magnetic resonance techniques, whether in neat
cycloalkanes or in dilute solutions in high-IP liquids. Only recently has it been understood
that rapid spin-lattice (T
1
) relaxation in the high-symmetry cycloalkane radical cations
precludes their detection using ODMR [70]. This relaxation is caused by dynamic
averaging between the nearly degenerate ground and excited states of the radical cations;
this degeneracy results from the JahnTeller distortion. For example, trans-decalin cation
isolated in room-temperature cyclohexane has T
1
<7 nsec [70]. Because it takes several
tens of nanoseconds to ip the electron spin for detection, radical cations of these
cycloalkanes cannot be detected by ODMR.
In the early studies, the cycloalkane holes were viewed as molecular radical cations
that undergo rapid resonant charge transfer. At any given time, the positive charge was
assumed to reside on a single solvent molecule and, once in 0.52 psec, to hop to a
neighboring molecule. The low activation energy was explained by the similarity between
the shapes of cycloalkane molecules and their radical cations [60].
This model is consistent with many observations. Dilution of cycloalkanes with high-
IP alkanes (or higher-IP cycloalkanes) results in a decrease in the hole mobility that
correlates with the mole fraction of the cycloalkane in the mixture: The hopping rate
decreases when the density of the like molecules decreases. The occurrence of resonant
charge hopping is rmly established experimentally. Charge transfer between c-C
6
D
12
+
and c-C
6
H
12
was observed in the gas phase, where it proceeds at 1/3 of the collision rate
[71]. The hopping was also observed for radical cations and molecules of cis- and trans-
decalins in dilute cyclohexane solutions (where it proceeds with a diusion-controlled rate)
[72]. In low-temperature solid hydrocarbons (430 K), hole hopping was observed by
ODMR [68]. At higher temperatures, the spectral diusion caused by the hopping causes
the ODMR spectrum to collapse to a single narrow line observed using magnetic level-
crossing and quantum beat spectroscopies [64,65].
On the other hand, matrix-isolation EPR and ab initio calculations suggest that
neutral cycloalkanes and their cations have rather dierent geometries. In cis- and trans-
decalins, the bridging bond elongates from 0.1530.156 nm in the neutral molecule to
0.190.21 nm in the radical cation [73]. Upon charging, the molecules undergo consid-
erable structural relaxation, losing 0.50.7 eV [73]. If the electron transfer were a single-
step process, it would require an activation energy of 12 eV. What then makes the
resonant charge transfer possible? In the gas phase, the electron exchange proceeds
through the formation of a collision complex in which the charge is shared by both of
the cycloalkane moieties [71]. This sharing considerably reduces the barriers for the
structural relaxation. It may be assumed that in liquid cycloalkanes the charge is shared
between several solvent molecules (analogous to the situation for solvent anions) and this
sharing further reduces the hopping barrier.
The sharing of charge causes delocalization of the hole. The best evidence for the
delocalization of cycloalkane holes was provided by large scavenging radii (>2 nm) in
cold methylcyclohexane [69] and by hole dynamics in cyclohexane-methylcyclohexane
mixtures [74]. While the addition of less than 510 vol.% of methylcyclohexane to
cyclohexane reduces both the d.c. conductivity signal and its decay rate, further addition
of methylcyclohexane yields little change in the conductivity signal and kinetics. The initial
reduction is accounted for by rapid reversible trapping of cyclohexane holes by methyl-
cyclohexane [74]. At higher concentration of methylcyclohexane, the equilibrium fraction
of the cyclohexane holes becomes very low and the conductivity should decrease.
Experimentally, the migration of methylcyclohexane hole in 5 vol.% methylcyclohexane
solution is as rapid as that of the solvent holes in neat methylcyclohexane. When the
methylcyclohexane is diluted by n-hexane instead of the cyclohexane, the conductivity
signal decreases proportionally to the fraction of n-hexane. These results suggest that the
methylcyclohexane holes are coupled to the cyclohexane solvent (the dierence in the
liquid IPs is <0.11 eV [74]). This coupling makes the charge migration of methylcyclo-
hexane holes in cyclohexane as ecient as in neat methylcyclohexane. From the critical
concentration of methylcyclohexane, the delocalization radius was estimated as 1 nm, or 4
to 5 molecular diameters [74]. Thus the degree of charge delocalization in cyclohexane (for
the hole) and hexauorobenzene (for the electron) are comparable.
We turn to the chemical behavior of cycloalkane holes. Several classes of reactions
were observed for these holes: (1) fast irreversible electron-transfer reactions with solutes
that have low adiabatic IPs (ionization potentials) and vertical IPs (such as polycyclic
aromatic molecules); (2) slow reversible electron-transfer reactions with solutes that have
low adiabatic and high vertical IPs; (3) fast proton-transfer reactions; (4) slow proton-
transfer reactions that occur through the formation of metastable complexes; and (5) very
slow reactions with high-IP, low-PA (proton anity) solutes.
Class (1) reactions were observed in all four cycloalkanes. The highest rate constants
were observed for reactions of cyclohexane hole with low-IP aromatic solutes, (34.5)
10
11
M
1
sec
1
at 25jC [75]. In these irreversible reactions, a solute radical cation is gen-
erated. Class (2) reactions were observed for reactants 1,1-dimethylcyclo-pentane, trans-1,
2-dimethylcyclopentane, and 2,3-dimethyl-pentane in cyclohexane [74], trans-decalin,
bicyclohexyl, and iso-propylcyclohexane in methylcyclohexane [69], and benzene in cis-
and trans-decalins [76] (Fig. 7). In these class (2) reactions, biexponential scavenging ki-
netics of the solvent hole results because of the dynamic equilibrium between the solvent
hole and the corresponding solute cation (in the latter case, the kinetics are complicated by
the subsequent dimerization of the benzene cation, Fig. 7). For methylcyclohexane in cy-
clohexane, the equilibrium is so rapidly reached that the decay kinetics are single expo-
nential at any temperature. Similar equilibria exist for high-mobility holes in mixtures of
cis- and trans-decalins.
The rate constants of the forward class (2) reactions are much slower than those of
the class (1) reactions, although some of electron donors have comparably low adiabatic
IP
g
s. These rate constants do not correlate with the free energies of hole scavenging
Figure 7 A typical reversible reaction of a cycloalkane hole. (a) Trans-decalin hole rapidly reacts
with benzene transferring positive charge to the solute. The reverse charge transfer reaction is relatively
slow (the free energy decreases by 200 meV), and the lifetime of benzene monomer is ca. 7 nsec. This
lifetime is further shortened by dimerization of the monomer; this dimerization shifts the equilibrium
to the right side. The charge transfer competes with slow, with the formation of decalyl radical and
benzoniumcarbocation by an irreversible proton transfer. (b) The populations of solute monomer and
dimer cations (e.g., benzene cations) can be tracked using a CTFS technique analogous to the electron
photodetachment technique discussed in the caption to Fig. 3c. Photoexcited solute radical cations
oxidize the solvent and their dynamics can be followed through the observation of increase in
conductivity because of generation of the high-mobility solvent hole; this increase is analyzed as a
function of the delay time of the excitation pulse (From Ref. 76.)
reactions obtained from the temperature dependencies of equilibria parameters [74]. An
explanation proposed was that the rate constants are controlled by the height of the
activation barrier determined by the dierence in the vertical IP of the solute and the
adiabatic IP of the solvent (Sec. 2) [74]. A similar mechanism accounts for the chemical
behavior of the high-mobility solvent radical anion in sc CO
2
(vide supra) [18].
Class (3) reactions include proton-transfer reactions of solvent holes in cyclohexane
and methylcyclohexane [71,74,75]. The corresponding rate constants are 1030% of the
fastest class (1) reactions. Class (4) reactions include proton-transfer reactions in trans-
decalin and cistrans decalin mixtures [77]. Proton transfer from the decalin hole to
aliphatic alcohol results in the formation of a C-centered decalyl radical. The proton
anity of this radical is comparable to that of a single alcohol molecule. However, it is less
than the proton anity of an alcohol dimer. Consequently, a complex of the radical cation
and alcohol monomer is relatively stable toward proton transfer; when such a complex
encounters a second alcohol molecule, the radical cation rapidly deprotonates. Metastable
complexes with natural lifetimes between 24 nsec (2-propanol) and 90 nsec (tert-butanol)
were observed in liquid cis- and trans-decalins at 25jC [77]. The rate of the complexation is
one-half of that for class (1) reactions; the overall decay rate is limited by slow proton
transfer in the 1:1 complex. The rate constant of unimolecular decay is (510) 10
6
sec
1
;
for primary alcohols, bimolecular decay via proton transfer to the alcohol dimer prevails.
Only for secondary and ternary alcohols is the equilibrium reached suciently slowly that
it can be observed at 25jC on a time scale of >10 nsec. There is a striking similarity
between the formation of alcohol complexes with the solvent holes (in decalins) and
solvent anions (in sc CO
2
).
A detailed analysis of the thermodynamics and energetics of the complexation
reactions is given in Ref. 77. The forward reaction has near-zero activation energy,
whereas the proton transfer within the complex is thermally activated (2025 kJ/mol). The
stability of the complex increases with the carbon number of the alcohol; the standard heat
of the complexation decreases in the opposite direction (from 39 kJ/mol for ethanol to
25 kJ/mol for tert-butanol). Complexes of cis-decalin
+
are more stable than complexes
of trans-decalin
+
because for the former, the standard reaction entropy is 35 J mol
1
K
1
more positive. The decrease in the entropy is small for both decalins (>80 J mol
1
K
1
)
and approaches zero for higher alcohols. Similarly small changes in the standard entropy
were observed for class (2) reactions of the methylcyclohexane hole [69]. Because the
molecular complex formation can only reduce the degrees of freedom, to account for the
small change in the entropy, there must be an increase in the solvent disorder. This is
consistent with a hole ordering solvent molecules around itself. When the positive charge is
compensated, the solvent becomes disordered, and the reaction entropy increases. The
same eect is expected to occur for all solvent radical ions considered in this chapter.
Extremely slow class (4) reactions were observed for scavenging of (a) cyclohexane
hole by cyclopropane [60] and (b) cyclohexane and decalins holes by O
2
[75]. H atom
transfer from the hole to O
2
and H
2
transfer from cyclopropane to the hole were suggested

as the possible reaction mechanisms.
In conclusion, the behavior of high-mobility solvent anions and cations is similar.
Both occur only in liquids whose molecules have rigid bodies and exhibit little or no
conformational dynamics. Neither occurs in liquids where solvent radical ions have a
strong tendency to form dimers with neutral solvent molecules. Both migrate by rapid
hoppingsometimes over the entire liquid range of the solventand involve charge
delocalization over several molecules. The activation energies and the degree of delocal-
ization are roughly the same. Delocalization is required for the hopping to be rapid
because it reduces geometric adjustment to charge placement and thereby decreases the
activation barrier for charge transfer. Both species rapidly react with electron donors/
acceptors with rate constants that are determined only by vertical IP
g
or EA
g
of the solute.
In nonpolar liquids, both species display a strong tendency to form metastable complexes
with polar molecules, such as alcohols and nitriles, in which the charge is electrostatically
bound to the solute dipole. With respect to this propensity, the high-mobility ions are
similar to solvated electrons in saturated hydrocarbons. Even in polar solvents, solvent
anions (e.g., the dimer anion in acetonitrile) are protonated only after formation of a
complex with the alcohol monomer; the transfer occurs when a second alcohol molecule
encounters the complex [30].
6. CONCLUDING REMARKS
The important lesson of this chapter is that there are many ways in which a charge can be
localized in a molecular system, and quite a few liquids localize electrons and holes in ways
that defy easy classication. One does not need to look far for such exotic systems;
ordinary solvents will do. In liquid acetonitrile [30,46], a high-energy electron state, a
cavity electron, coexists in a dynamic equilibrium with a low-energy state, a dimer radical
anion. In liquid benzene [45], the negative charge can migrate both by thermal emission
into the CB and by degenerate electron hopping, depending on the pressure. Actually,
most liquids seem to exhibit unique charge dynamic properties; there are few general rules.
In the previous four sections, several solvent radical ions that cannot be classied as
molecular ions (a charge on a solvent molecule) were examined. These delocalized,
multimer radical ions are intermediate between the molecular ions and cavity electrons,
thereby bridging the two extremes of electron (or hole) localization in a molecular liquid.
While solvated electrons appear only in negative-EA
g
liquids, delocalized solvent anions
appear both in positive and negative-EA
g
liquids. Actually, from the structural standpoint,
trapped electrons in low-temperature alkane and ether glasses [2] are closer to the
multimer anions because their stabilization requires a degree of polarization in the molec-
ules that is incompatible with the premises of one-electron models.
How general is the formation of multimer solvent ions? We reiterate the argument
made in Sec. 3 that very few systems apart from water, alcohols, saturated hydrocarbons,
and ethers have been studied by pulse radiolysis and laser photolysis, and for most of these
liquids the ionic species observed were not primary ions. The incidence of high-mobility
primary ions among neat organic liquids is actually high. It should also be kept in mind
that if a given liquid does not yield high-mobility solvent ions under normal conditions,
this does not necessarily hold for other conditions. High-mobility solvent anions in sc CO
2
occur only in the supercritical phase [18,20]; in the cold liquid, the binding of the dimer
anion core is too strong for the rapid charge hopping to occur. High-mobility solvent
anions in benzene [45] are observed only under high-pressure conditions, etc. Further-
more, as discussed above, many organic liquids yield solvent ions that are short-lived (<
10 nsec), and their dynamic properties cannot be studied using existing pulse radiolysis
techniques. Finally, only in a small subset of liquids (whose molecules have rigid bodies
and whose ions do not dimerize) can the delocalization of the excess charge be observed
through faster-than-Brownian-diusion hopping.
The authors believe that the formation of peculiar solvent ions is common;
however, only in a handful of cases can one clearly demonstrate that such ions are
formed. Far from being exotic species, these ions may constitute the rule, whereas the
textbook species, solvated electrons and molecular ions, could be rare exceptions. That
these exceptions loom large in the collective mind of chemical physicists is because
aqueous solutions surround us in everyday life, and most radiation chemistry studies
have been carried out on aqueous solutions at 25jC. If human beings were made of sc
CO
2
, hydrated electrons would be considered marginal and exotic. An alien living in an
acetonitrile ocean would be correct in pointing out that terrestrial radiation chemists pay
too much attention to water, whose properties are unique. An intelligent bacterium living
in a hydrothermal vent would have diculty understanding our interest in the normal
conditions. In short, radiation chemistry, as we know it, is biased. Arguably, overcoming
this bias, by expanding the range of physical conditions and the number of systems
studied, will rejuvenate the twenty-rst century radiation chemistry.
ACKNOWLEDGMENT
The preparation of this review was supported under contract No. W-31-109-ENG-38 with
US-DOE Oce of Basic Energy Sciences, Division of Chemical Sciences.
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12
The Radiation Chemistry of Liquid Water:
Principles and Applications
G. V. Buxton
University of Leeds, Leeds, England
SUMMARY
An overview of the radiation chemistry of water is given from the start of its systematic
study some 60 years ago to the present day. Attention is conned to the eects of low
linear energy transfer (LET) radiation at ambient temperature and pressure because these
are the conditions most commonly used in the application of water radiolysis as a tool in
general chemistry. After a brief historical perspective, a scheme for the radiation chemistry
of water is presented together with a review of recent results of stochastic and deterministic
modelling of the spur reactions that occur between 10
12
and 10
7
sec. This is followed by
a detailed discussion of the evolution of the yields (G-values) of e
aq
, H
.
,
.
OH, H
2
, and
H
2
O
2
resulting from the spur reactions and how they are measured using scavengers, or
by direct observation using pulse radiolysis. Next, the physical and chemical properties of
e
aq
, H
.
, and
.
OH are presented, followed by methods of converting these primary radicals
to secondary ones of a single kind, either oxidizing or reducing, and covering a wide range
of reduction potentials. From this information, one can determine what G-values to use
for the radicals and can tune the reduction potential for the chemical system of interest.
Finally, reference is made to a recently published textbook [Radiation Chemistry. Present
Status and Future Prospects, Jonah, C. D., Rao, B. S. M., Eds.; Elsevier: Amsterdam,
2001] that gives details of the wide range of chemical studies that have been made using
water radiolysis as a tool.
1. HISTORICAL PERSPECTIVE
Systematic studies of the eects of ionizing radiation on liquid water began in earnest in the
1940s, at the University of Chicago [1], as part of the work on the atomic bomb project. This
project involved building a nuclear reactor to produce plutoniumand, because of its neutron
absorption cross-section, fast-owing water was deemed to be the best method for cooling
the reactor. Fast neutrons knock out protons from water molecules and these energetic
charged particles ionize and excite further molecules to produce a multitude of free electrons
and positively charged species. The ejected electrons themselves can also have sucient
energy to cause ionization and excitation of water molecules. Qualitatively, whether the
energetic particle is a fast neutron, charged particle, or photon (i.e., x-ray or g-ray), the result
is that a single interaction of such a particle causes several water molecules to be ionized or
excited. These initial events are classed as radiation physics. The radiation chemistry
comprises the sequence of events that lead to the nal products of water decomposition
resulting from the ionization and excitation processes. The yields of these nal products do,
however, depend on the nature of the original energetic particle. As will be seen later, this
sequence of events is divided into a physicochemical stage, during which the initial products
reach thermal equilibrium with the liquid, followed by a kinetically nonhomogeneous
reaction stage.
The idea that ionizing radiation decomposes water into hydrogen atoms and hydroxyl
radicals according to reaction (1) was suggested rst by Risse [2] in 1929 and later by Weiss
[3] in 1944:
H
2
OQH
.
.
OH 1
In 1938, Fricke et al. [4] had shown that although x-rays seemed not to decompose pure
water, they caused oxidation and reduction to take place in aqueous solutions. On the other
hand, it was also known from the earliest days of radiochemistry that a-rays decompose
liquid water to H
2
, O
2
, and H
2
O
2
. This dependence of the decomposition of water on the
linear energy transfer (LET) of the ionizing radiation was rst explained by Allen [5], who
put forward the concept that the molecular products are formed in tiny regions of high
radical concentrations, so-called spurs, along the track of the ionizing particle. Essen-
tially, there is a competition between the back reactions of the radicals in the spurs to form
the molecules H
2
, H
2
O
2
, and H
2
O, and their escape by diusion into the bulk liquid. This led
to the development of the spurdiusion model (see Section 2 below) and was a major
contribution to the understanding of the radiation chemistry of water, which at that time
was represented by reaction (2):
H
2
OQH
.
;
.
OH; H
2
; H
2
O
2
2
The yields of these so-called primary species, present at the time when radical combina-
tion in, and diusive escape from, the spurs is complete, were obtained by adding solutes to
the water to capture the radicals and by measuring the stable identifying products. It was
from a number of these studies that it became clear that the reducing radical must exist in
two forms, which turned out to be the hydrogen atom and the hydrated electron (e
aq
). For
example, Hayon and Weiss [6] found that the yields of H
2
and Cl
produced by irradiating
solutions of chloroacetic acid varied with pH in a manner that was consistent with the
following reactions:
e
aq
H
! H
.
3
e
aq
ClCH
2
CO
2
H ! Cl

.
CH
2
CO
2
H 4
H
.
ClCH
2
CO
2
H ! H
2

.
CHClCO
2
H 5
It is now generally agreed that for low LET radiation, such as x-rays, g-rays, and fast elec-
trons, the radiolysis of water can be represented to a good approximation by reaction (6):
4:36H
2
OQ2:8e
aq
; 0:62H; 2:8OH; 0:47H
2
; 0:73H
2
O
2
; 2:8H
6
The numbers in reaction (6) are the so-called primary yields (expressed here in units of
10
7
mol J
1
) of the radical and molecular products that are present when the spur processes
are complete at ca. 10
7
sec. The original units for these yields, which are still in use, are
molecules (100 eV)
1
, and the relationship between the two sets is 1 mol J
1
u9.6510
6
molecules (100 eV)
1
. Thus, reaction (6) may also be written as reaction (7):
4:2H
2
OQ2:7e
aq
; 0:6H; 2:7OH; 0:45H
2
; 0:7H
2
O
2
; 2:7H
7
In this chapter, the various radiation chemical yields, known as G-values, are dened as
follows: g(X) is the yield of the species in reactions (6) and (7); G
o
(X) is the yield of the initial
products of water radiolysis at the end of the physicochemical stage; and G(X) is an
experimentally measured yield. In some publications G
X
, rather than g(X), is used to
represent the primary yield of the species X. The yields in reactions (6) and (7) are
numerically very similar, but one must be sure of the units that are being used to express
them. In the older literature, it was common practice to quote G-values without units when
the units were in fact molecules (100 eV)
1
.
Shortly after the discovery of the hydrated electron, Hart and Boag [7] developed the
method of pulse radiolysis, which enabled them to make the rst direct observation of this
species by optical spectroscopy. In the 1960s, pulse radiolysis facilities became quite widely
available and attention was focussed on the measurement of the rate constants of reactions
that were expected to take place in the spurs. Armed with this information, Schwarz [8]
reported in 1969 the rst detailed spurdiusion model for water to make the link between
the yields of the products in reaction (7) at ca. 10
7
sec and those present initially in the spurs
at ca. 10
12
sec. This time scale was then only partially accessible experimentally, down to ca.
10
10
sec, by using high concentrations of scavengers (up to ca. 1 mol dm
3
) to capture the
radicals in the spurs. Fromthen on, advancements were made in the time resolution of pulse
radiolysis equipment from microseconds (10
6
sec) to picoseconds (10
12
sec), which
permitted spur processes to be measured by direct observation. Simultaneously, the increase
in computational power has enabled more sophisticated models of the radiation chemistry
of water to be developed and tested against the experimental data.
More generally, water radiolysis provides a very versatile method of generating other
free radicals and unstable intermediates such as hyperreduced metal ions. This, when
combined with the technique of pulse radiolysis, has, without doubt, made an enormous
contribution to our knowledge of one-electron redox chemistry in aqueous inorganic,
organic, and biochemical systems that cannot be studied readily by thermal or photo-
chemical methods. Most commonly, this means using radiation of low LET such as
60
Co g-
rays or beams of high-energy electrons. The eects of increasing LETand/or temperature on
the chemical stage of water radiolysis are covered in Chaps. 14 and 23, respectively.
In this chapter, an outline of the radiation chemistry of water is given in Section 2.
Section 3 describes how the yields of the radical and molecular products evolve with time,
and indicates the bounds of useful experimental conditions for the use of water radiolysis as
a tool in general chemistry. In these two sections, emphasis is placed on recent developments
in modelling experimental data that shed newlight on our understanding of the fundamental
aspects of water radiolysis. Section 4 contains a summary of the chemical and physical
properties of the primary radicals. In Section 5, examples are given to show how these
radicals can be converted into secondary radicals, often of a single kind. This is an important
consideration for the study of the chemistry of free radicals and metal ions in unusual
oxidation states. Finally, reference is given in Section 6 to examples of applications that have
resulted in signicant advances being made in general chemistry.
2. SCHEME FOR THE RADIATION CHEMISTRY OF WATER
The approximate time scale of events initiated by the absorption of energy by water fromthe
incident ionizing radiation is shown in the following scheme:
Initially, a water molecule is ionized or electronically excited in about 10
16
sec or less,
depending on the energy of the particle causing the ionization. The ejected electron generally
has sucient energy to ionize or excite further water molecules. This process continues until
the energy of the ejected electron is no longer sucient to raise a water molecule above its
ground electronic state. This so-called subexcitation electron loses the rest of its excess
energy by exciting vibrational and rotational modes of the solvent molecules.
At the end of the physical stage, which is within about 10
16
sec of the passage of the
ionizing particle through the liquid, the track made by the particle contains H
2
O
+
,
subexcitation electrons e
se
, and electronically excited water molecules H
2
O* in small clusters
called spurs. From about 10
16
to 10
12
sec, the following processes are thought to occur
and comprise the physicochemical stage [9,10]:
H
2
O
se
! H
2
O
vib
*
I
H
2
O
vib
*
H
.
.
OH
H
2
O
.
1
D ! H
2
H
2
O
2
or 2
.
OH
2H
.
O
.
3
P
Ia
Ib
Ic
H
2
O
H
2
O ! H
aq

.
OH II
e
se
H
2
O !
.
OH H
!
.
OH H
2
OH
III
e
se
H
2
O ! e
aq
IV
H
2
O
elec
*
.
OH H
.
H
2
O
.
1
D ! H
2
H
2
O
2
or 2
.
OH
2H O
.
3
P
Va
Vb
Vc
Processes (I) and (II) account for H
2
O
+
, whereas processes (I), (III), and (IV) describe the
fate of e
se
. According to Kaplan et al. [11], process (I) produces water molecules in high
vibrational levels of their electronic ground state. The remaining H
2
O
+
reacts with water to
form H
aq
and
.
OH in process (II). This ionmolecule reaction is known to occur in the gas
phase with a rate constant of 810
12
dm
3
mol
1
sec
1
[12], which, when extrapolated to
liquid water, sets the lifetime of H
2
O
+
in this medium at less than 10
14
sec. However,
Hamill [13] pointed out that H
2
O
+
initially has the structure of a neutral water molecule so
that it may migrate rapidly over distances of a fewmolecular diameters by resonant electron
transfer with a succession of neighboring water molecules.
The subexcitation electrons that escape process (I) either undergo a dissociative
attachment to H
2
O as in process (III), or thermalize and become solvated (process (IV)).
Process (III), which is important in the gas phase, was suggested by Platzman [14] and
Faraggi and Desalos [15] to be responsible for an apparently unscavengeable yield of
molecular hydrogen in the radiolysis of liquid water. That a precursor of the hydrated
electron is the source of at least part of G(H
2
) has been established by the nding that
scavengers such as selenate ion, dichromate ion, and nitrate ion, which are known to react
eciently with a precursor of the hydrated electron (see Section 3.1.1), lower G(H
2
) to near
zero at suciently high concentrations, for both low[16] and high [17] LET radiation. It has
also been shown that when water is photoionized using a subpicosecond laser pulse [18],
process (IV) occurs in less than 10
12
sec.
Very little is known about the decay channels for excited water molecules in the liquid
phase. Consequently, they are generally assumed [9,10] to be essentially the same as those in
the gas phase.
2.1. Modelling
In recent years, two dierent approaches, deterministic [9,19] and stochastic [10,20], have
been used with a good level of success to model the radiation chemistry of water. Each
approach leads to reasonable agreement between calculated results and experimental data
obtained for a wide range of LET fromroomtemperature up to ca. 300jC[9,10]. There are,
however, fundamental dierences between the two models. The deterministic model is based
on the concept of an average spur [8,9,19,23] at the end of the physicochemical stage (ca.
10
12
sec), which contains the products of processes (I), (II), (III), (IV), and (V) in certain
yields and spatial distributions, and in thermal equilibrium with the liquid. For low LET
radiation, the spurs are treated as isolated spheres with usually a Gaussian distribution of
each species, and for high LETas continuous cylindrical tracks with a Gaussian distribution
having pseudo-two-dimensional symmetry. The initial yields ( G
o
) of the species and the
width of their spatial distributions are chosen to t with the experiment, but the two sets of
parameters are not independent [24]. The nonhomogeneous kinetics of the spur processes of
reaction and diusion is treated as a set of coupled dierential equations, which are solved
numerically.
The stochastic model [10,20] uses Monte Carlo simulations of the events that take
place during the physical stage up to ca. 10
15
sec, which, in principle, lead naturally to the
spatial distributions at the end of the physicochemical stage (ca. 10
12
sec). However,
assumptions have to be made about the energy loss processes of the incident ionizing
radiation and the secondary electrons that are thereby generated because these processes are
not well known quantitatively for liquid water. As in the deterministic approach, the
parameters are adjusted to give a t with experiment. Thereafter, the nonhomogeneous
reaction kinetics between ca. 10
12
and 10
6
sec is treated by the method of Independent
Reaction Times (IRT) [25]. This method assumes that the reaction time of each pair of
reactants is independent of the presence of other reactants in the system. The important spur
reactions are listed in Table 1.
The major dierence between the deterministic and stochastic methods lies in the
spatial distributions, and their dependence on temperature, of the species at the end of the
physicochemical stage (ca. 10
12
sec). As mentioned above, the spatial distribution is
assumed to be Gaussian in the deterministic approach. For G
o
(e
aq
) = 4.78 molecules
(100 eV)
1
, which is the value derived by Schwarz [8], the best t to the experimental data
was obtained with the width parameter r
o
of the Gaussian distributions at 25jC ca. equal
to 2.3 nm [9] or 2.23 nm [19] for e
aq
and the products of processes (Ia)(Ic), and 0.85 nm for
the other species [9,19]. It was later shown [24] that for G
o
(e
aq
) = 4.1 molecules (100 eV)
1
(see Section 3.2.1), a good t could be obtained by increasing r
o
for e
aq
to 3.8 nm. In contrast
to this, a recent version of the stochastic model [10] generates a very asymmetrical
distribution of hydrated electrons with most probable and average thermalization dis-
tances (equivalent to r
o
) of
f
2.5 and 9.2 nm, respectively at 25jC, and G
o
(e
aq
) = 5.3
Table 1 Reaction Scheme of the Chemical Stage in Water Radiolysis at 298 K for Low LET
Radiation
Symbol Reaction k/10
10
dm
3
mol
1
sec
1 a
DG/molecule (100 eV)
1 b
R1 e
aq
+H
+
!H
.
2.3 0.55
R2 e
aq
+
.
OH!OH
3.0 1.15
R3 H
+
+OH
!H
2
O 14.0
c
0.65
R4 e
aq
+e
aq
!H
2
+2OH
2k=1.1 0.27
R5 e
aq
+H
.
!H
2
+OH
2.5 0.10
R6 H
.
+H
.
!H
2
2k=1.5 0.007
R7 H
.
+
.
OH!H
2
O 1.5
d
0.16
R8
.
OH+
.
OH!H
2
O
2
2k=1.1 1.53
R9 e
aq
+H
2
O
2
!
.
OH+OH
1.1 0.07
a
Source: Ref. 59.
b
DG is the change in yield of e
aq
, H
.
, or
.
OH for each reaction between 10
12
and 10
6
sec predicted by the
deterministic model [9].
c
Source: Laidler, K.J. Chemical Kinetics; McGraw-Hill, New York, 1965.
d
Source: Ref. 63.
molecules (100 eV)
1
at 10
12
sec. The model predicts that G(e
aq
) has decreased by 11.6%to
4.7 molecules (100 eV)
1
at 10
10
sec, which is about the shortest time at which experimental
measurements have been made. In an earlier version [20], it was recognized that the initial
distribution would be asymmetrical but would rapidly become Gaussian through Brownian
motion. The initial distribution was therefore assumed to be Gaussian for convenience.
The best t with experiment was obtained with r
o
= 4 nm and G
o
(e
aq
) = 4.93 molecules
(100 eV)
1
. This version [20] also predicts G(e
aq
) =4.9 and 4.7 molecules (100 eV)
1
at 10
12
and 10
10
sec, respectively, a fall of only 2.1%.
In their deterministic modelling, Swiatla-Wojcik and Buxton [9] scaled the change in
the initial spur radii r
o
with temperature t using Eq. (8):
r
o
t r
o
25
j
Cq25
j
C=qt
1=3
8
where q is the density of water. The use of Eq. (8) results in r
o
increasing by no more than
11.5%up to 300jC. In the stochastic model [10], the temperature dependence of the electron
thermalization distance r
th
was deduced from considerations of g(H
2
), which was found to
be the yield most sensitive to r
th
. The best t with the experiment was obtained using Eq. (9):
r
th
300
j
C r
th
25
j
C=2 r
th
t decreasing linearly with t 9
Herve du Penboat et al. [10c] suggested that g-values at 300jC calculated using the
deterministic approach [9] would not be sensitive to a 50% decrease in r
th
, whereas when
this condition is imposed, it is found [26] that g(e
aq
) decreases from 3.410
7
to 2.810
7
mol J
1
, which is a signicant change. On the other hand, the g-values of the other products
are changed only slightly, the change being within the error of the measured values.
As would be expected, these results indicate that the thermalization distances and
spatial distribution of the hydrated electron are key parameters in modelling the radiation
chemistry of water. Although the stochastic approach is the more logical one to adopt, its
present status does not appear to outweigh the advantages of using the simpler deterministic
model to represent the essential features of water radiolysis over a wide range of conditions.
Before leaving the topic of modelling, it is pertinent to note that, at roomtemperature,
the deterministic model [9] and the stochastic model [10b] both predict that ca. 50%of g(H
2
)
comes fromthe sumof reactions (R4) and (R5), and negligible amounts fromreaction (R6).
The values for the deterministic model are given in Table 1. The corresponding values for the
stochastic model are 0.24 and 0.15 molecules (100 eV)
1
, respectively [10,b,], and 0.28 and
1
, respectively [20]. On the other hand, g(H
2
O
2
) is predicted to be
almost entirely accounted for by reactions (R8) and (R9) in both types of model.
3. YIELDS FOR LOW LET RADIATION
Water radiolysis has proven to be a very useful method of generating free radicals whose
reactions can be studied in a wide range of aqueous solutions. Indeed, a wealth of kinetic [27]
and mechanistic data has been obtained in this way, almost invariably using low LET
radiation, such as
60
Co g-rays for continuous radiolysis and high-energy electron beams
for pulse radiolysis. An important quantity in this kind of work is the yield of the radical
or molecule under investigation because it is dependent on the experimental conditions. The
g-values in Eqs. (6) and (7) have been derived from numerous scavenging studies where
the scavenging power, which is dened as k
(X+S)
[S], is typically ca. 10
7
sec
1
, is generally
appropriate for studies of the radiolysis of dilute aqueous solutions on the order of
10
3
mol dm
3
. In more concentrated solutions, one needs to consider scavenging by the
solute of e
aq
, H
.
, and
.
OH within the spurs, whereas in very dilute solutions, possible
depletion of the solute has to be taken into account. As will become clear in the following
section, scavenging studies have played an important role in our current understanding of
the chemical stage of water radiolysis.
Ageneralized reaction scheme for intraspur scavenging is represented by the following
reactions, using the principal radicals e
aq
and
.
OH in neutral water as examples:
e
aq
S
1
! P
1
10
.
OH S
2
! P
2
11
e
aq
P
2
! S
2
12
.
OH P
1
! S
1
OH
13
where S and P represent scavenger and product, respectively. As noted above, the
eectiveness of a given scavenging solute S is measured by its scavenging power, which,
for reactions (10) and (11), is k
10
[S
1
] and k
11
[S
2
] sec
1
, respectively. In principle, therefore,
data for dierent S can be normalized in terms of their scavenging power; in practice,
however, this procedure is not always valid. One reason for this is that when a single
scavenger is present, the product of the scavenging reaction (e.g., reaction (10) for e
aq
) may
react to some extent with the sibling radical
.
OHin reaction (13). In such a case, G(P
1
) will be
smaller than the scavenged yield of e
aq
. A second reason is that some scavengers may react
with a precursor of e
aq
, but at relative rates dierent from those for their reactions with e
aq
itself. Examples of such behavior are described in the following sections.
Although the time dependence of G(e
aq
) and G(
.
OH) can be obtained by direct
observation using pulse radiolysis, as well as by adding scavengers, the evolution of the
yields of H
.
, H
2
, and H
2
O
2
can only be derived from scavenger studies.
3.1. The Molecular Yields G(H
2
) and G(H
2
O
2
)
G(H
2
)
In dilute aqueous solution, g(H
2
) = 0.45 molecule (100 eV)
1
is well established. In more
concentrated solutions of certain solutes, G(H
2
) decreases as the concentration of solute
increases, showing that precursors of H
2
are being scavenged. The question to be answered
is: Which are the relevant precursors? According to the scheme presented in Section 2, the
possibilities are e
sec
, H
2
O*, H
, e
aq
, and H
.
. Several studies have been made in attempts to
answer this question; the main ideas are summarized below.
Faraggi and Desalos [15] showed that G(H
2
) is independent of [S
1
] for S
1
=Ni
2+
,
Co
2+
, and Zn
2+
although these cations all react eciently with e
aq
. They concluded,
therefore, that H
, rather than e
aq
or H
.
, is the main precursor of H
2
. On the other hand,
Peled and Czapski [28] investigated the eects on G(H
2
) of high concentrations of reactive
anions and neutral molecules as well as cations, and concluded that e
aq
is the main precursor
through reactions (R4) and (R5) in Table 1. The apparent conict with the results of Faraggi
and Desalos [15] for S
1
= Ni
2+
, Co
2+
, and Zn
2+
was eectively resolved by adding 10
3
mol dm
3
NO
3
to the solutions and allowing for the eect of ionic strength on k
10
. The role
of NO
3
is to oxidize the M
+
formed in reaction (10) back to M
2+
to prevent the possibility
of H
2
being produced in further reactions of M
+
. Peled and Czapski [28] also showed that
the results for anions, neutral molecules, and cations as scavengers for e
aq
could be brought
into near coincidence on a single curve of G(H
2
) vs. log(k
10
[S
1
]) when ionic strength eects
were properly taken into account.
The idea that e
aq
is the main precursor of H
2
was supported by results obtained by
Draganic and Draganic [29]. These are exemplied in Fig. 1, which shows that measure-
ments made of the ratios G(H
2
)/g(H
2
) and G(H
2
O
2
)/g(H
2
O
2
) as a function of scavenging
power for a number of dierent scavengers fall very close to a single curve. Draganic and
Draganic [29] also found that when S
1
and S
2
are both present, raising [S
1
] at xed [S
2
] causes
G(H
2
O
2
) to increase; the corresponding eect is also observed for G(H
2
). These results
seemed to provide clear evidence that scavenging in the spurs of one of the primary radicals
promotes the self-reaction of the other one.
Recent studies by Pastina et al. [16] of solutes having a wider range of reactivity toward
the hydrated electron demonstrate that the single scavenging curve shown in Fig. 1 is not
always obtained. Some of the results reported [16], which illustrate this point, are shown in
Fig. 2. Here, the left-hand set of points is plotted against the scavenging power of S
1
for e
aq
,
whereas the right-hand set is plotted against the scavenging power of S
1
for the precursor(s)
of e
aq
, designated here as e
pre
. There is much less scatter in the right-hand set of data, which
led Pastina et al. [16] to conclude that the yield of molecular hydrogen is better para-
meterized by the scavenging capacity for the precursors to the hydrated electron than by the
scavenging capacity for the hydrated electron. In determining the rate coecients for the
reactions of the precursor of e
aq
, Pastina et al. [16] used a procedure outlined previously by
Pimblott and LaVerne [30]. However, for the same scavengers, Pastina et al. [16] quote
values for the rate coecients that are quite dierent from those reported by Pimblott
and LaVerne [30]. The dierence is greatest for H
2
O
2
, with values of zero [30] and 6.33 10
13
dm
3
mol
1
sec
1
[16], but there are signicant dierences between the values for other
solutes. Pastina et al. [16] concluded that process (III) could make a signicant contribution
to g(H
2
) in the radiolysis of water (reaction (7)). Similarly, a good agreement among SeO
2
4
,
Cr
2
O
2
7
, and H
2
O
2
has been obtained with high LET radiation [17] where g(H
2
), as is well
Figure 1 Decrease of G(H
2
)/g(H
2
) or G(H
2
O
2
)/g(H
2
O
2
) with increasing reactivity toward e
aq
or
.
OH. For H
2
: S
1
=H
2
O
2
+10
3
mol dm
3
Br
(o); NO
3
+510
4
mol dm
3
I
(5); Cu
2+
+10
3
mol
dm
3
Br
(D).For H
2
O
2
: S
2
jC
2
H
5
OH+2.510
3
mol dm
3
NO
3
(
.
). (From Ref. 29.)
known, is larger. However, process (III) is kinetically rst-order, whereas the increase in
g(H
2
) with increasing LET is expected to involve second-order processes because the local
concentration of radiolysis products also increases with LET. On the basis that the lifetime
of H
2
O
+
is on the order of 10
13
sec, rather than 10
14
sec (see Section 2), LaVerne and
Pimblott [17] concluded that process (I), followed by process (Ib), is even more signicant
than process (III) as a source of the yield of molecular hydrogen. These results imply that the
precursor of e
aq
is scavenged while it still has excess energy [17].
The sources of g(H
2
) according to deterministic [9] and stochastic [10] modelling are
processes (I), (III), and (V) and also the spur reactions (R4) (R5) (R6). As shown in Table 1,
the deterministic model indicates that approximately 50% of g(H
2
) is produced in reactions
(R4) and (R5), and similar results are predicted by the stochastic model [10b,20]. The models
also predict that the extent of reactions (R4) and (R5) increases with LET. For an increase in
LET from 0.2 to 60 eV nm
1
, g(H
2
) increases to 0.27 and 0.42 molecules (100 eV)
1
due to
reactions (R4) and (R5), respectively [21]. These data, together with numerous experimental
results, are not consistent with the conclusion [17] that H
2
is generated mainly through
reaction of e
se
with H
2
O
+
. There will, of course, be no e
aq
produced under conditions where
e
se
is scavenged eciently in suciently concentrated solution. However, it does not follow
that reactions (R4) and (R5) do not contribute to g(H
2
) in dilute solution or pure water.
Reactions of e
pre
. It is convenient to consider these reactions here. That the electron
can react with solutes before it becomes solvated is clearly demonstrated by the data in
Fig. 3, which were obtained by picosecond pulse radiolysis [31]. The data show that there is
no good correlation between the C
37
value of a solute and its rate constant k for reaction
with e
aq
measured at the same high concentrations of solute used to determine C
37
. The
parameter C
37
is the concentration of solute that lowers the earliest measurable value of
G(e
aq
) to 37% of the value obtained in the absence of solute. A linear correlation between
C
37
and k would be expected if the solute merely reacted with e
aq
before this earliest time of
Figure 2 Decrease of G(H
2
) with increasing reactivity toward e
aq
(left-hand data set) and its
precursor, e
(right-hand data set). S

1
= H
2
O
2
(z); SeO
2
4
(n); MoO
2
4
(.); Cr
2
O
2
7
(o). (From Ref.
16.) The left-hand set includes data for S
1
= H
2
O
2
from Figure 1 for comparison (q).
measurement (50 psec). Such a correlation was reported originally by Lam and Hunt [32];
the straight line of slope 1 in Fig. 3 ts quite closely their data for several solutes. The
notable exception is H
+
.
It is now known that there are a number of dierent states in which the precursors
e
pre
of e
aq
exist [33]. Recent studies [33] show that, using a static scavenging model, the
eciencies with which these precursors are scavenged are very similar for NO
3
, Cd
2+
, and
SeO
2
4
, whether the energized state is reached by multiphoton ionization of water,
photoionization of FeCN
4
6
, optical excitation of e
aq
, or ionization of H
2
O by radiolysis.
These results are considered to be consistent with there being no energy barrier to the
transfer of the electron due to the high exoergicity of these reactions and the availability
of open electronic and vibrational channels involving excited states of the scavenger [33].
Kee et al. [33] showed that the rate constant for reaction of the precursors of e
aq
with NO
3
,
Cd
2+
, and SeO
2
4
is inversely proportional to the volume of e
pre
. On this basis, they obtained
a best-t value of 9.0210
13
sec
1
for the static scavenging rate constant for e
aq
(i.e., the rate
of the scavenging reaction when e
aq
is within the reaction distance of a scavenger molecule).
An anomaly in the radiolysis results was noted by Kee et al. [33]. This disappears when rate
coecients for e
pre
from Ref. 30, which were used by Kee et al. [33], are replaced by those
from Ref. 16.
G(H
2
O
2
)
There seems to be little doubt from modelling [9,10,19,20] and experimental results (see
Fig. 1) that the major precursor of the molecular yield of H
2
O
2
is
.
OHthrough reaction (R8)
in Table 1. That reaction (R8) is a more important spur reaction than reactions (R4) and
Figure 3 Dependence of C
37
on k(e
aq
+S
1
) obtained at [S
1
]=C
37
mol dm
3
. Ref. 32: open points;
Ref. 31: solid points.
(R5) is consistent with
.
OHhaving a narrower spatial distribution than e
aq
. The unied curve
for G(H
2
)/g(H
2
) and G(H
2
O
2
)/g(H
2
O
2
) in Fig. 1 may therefore be a somewhat fortuitous
result of the spatial distributions of the radicals and the rate constants of their reactions with
one another. If, as proposed by LaVerne and Pimblott [17], process I(b) is an important
contributor to g(H
2
), then there should also be a signicant initial yield of H
2
O
2
resulting
fromthe reaction of O
.
(
1
D) with H
2
O, but there is no experimental evidence for such a yield.
3.2. G(e
aq
)
Numerous measurements have been made of g(e
aq
) for lowLET radiation and most of these
have been carried out under steady-state conditions using dilute (ca. 10
3
mol dm
3
) solu-
tions of a suitable scavenger S
1
to form an identiable stable product P
1
, as in reaction (10).
As the scavenging power k
10
[S
1
] increases, G(P
1
) also increases because reaction (10) com-
petes with other reactions of e
aq
in the spur (see Table 1). Fromtheir extensive results on spur
scavenging, Draganic and Draganic [34] obtained unifying curves that describe the depend-
ence of the fractional changes in the radical and molecular yields G(X)/g(X), on scavenging
power. These curves are reproduced in Figs. 4 and 5. Draganic and Draganic [34] concluded
on the basis of these results that secondary spur reactions such as reactions (12) and (13) are
not signicant for the scavengers they studied. Moreover, their data showed [34] that
ecient scavenging of e
aq
not only increases G(P
1
) in reaction (10) but also increases G(
.
OH)
by reducing the extent of water reformation (see Table 1) and releasing more
.
OH for other
reactions such as reaction (11) when the solution contains S
2
as well as S
1
. This condition
is known as cooperative scavenging. Similarly, the scavenging of
.
OH in reaction (11) leads
not only to an increase in G(P
2
) but also in G(e
aq
). The results obtained by Draganic and
Draganic [34] are presented in Figs. 4 and 5.
Other data for a number of dierent scavengers showing the eect on G(P
1
) of
increasing the concentration of the scavenger S
1
are reproduced in Fig. 6 for nitrous oxide
Figure 4 Dependence of the fractional yields G(X)/g(X) of the primary products of water
radiolysis (see reaction (7)) on the scavenging power of S
1
. (From Ref. 34.)
Figure 6 Comparison of experimental and predicted values of G(P
1
) from electron scavenging as a
function of the scavenger power k
10
[S
1
]. S
1
= N
2
O (n); CH
3
Cl (E); C(NO
2
)
4
(x); glycylglycine (.);
NO
3
(o). The broken line is predicted from direct observation of the time dependence of G(e
aq
) in
pulse radiolysis experiments. (From Ref. 49.) The solid line is the t obtained by Pimblott and
LaVerne [43] with the restriction that G
o
(e
aq
1
.
Figure 5 Dependence of the fractional yields G(X)/g(X) of the primary products of water
radiolysis (see reaction (7)) on the scavenging power of S
2
. (From Ref. 34.)
[3537], methyl chloride [38,39], nitrate ion [29,40], glycylglycine [41], tetranitromethane
[37], and methyl viologen [40]. Contrary to the unifying curve obtained [34] for e
aq
in Fig. 4,
the data in Fig. 6 show considerable scatter, which is probably at least partially due to
scavenging of electrons in their presolvated state as discussed in Section 3.1. Note that G(P
1
)
continues to fall as k
10
[S
1
] is decreased below 10
6
sec
1
.
The rst attempt at providing a mathematical formulation of the eect of scavengers
on G-values in aqueous solution was made by Balkas et al. [38] based on an equation
developed by Warman et al. [42] for scavenging of ion pairs in nonpolar liquids. Balkas et al.
[38] showed that the yield of chloride ion from reaction (14) can be represented by Eq. (15):
e
aq
CH
3
Cl !
.
CH
3
Cl
14
GCl
2:55
2:23kS=k
1=2
1 kSk
1=2
15
In Eq. (15), g(e
aq
) =2.55 molecules (100 eV)
1
, G
o
(e
aq
1
, and k is
a constant estimated [38] to be 810
8
sec
1
. The term (k[S]/k)
1/2
/(1+(k[S]/k)
1/2
) is referred
to as the scavenger function F(S). The value of G
o
(e
aq
) was chosen to agree with the value of
Schwarz [8]. The value of g(e
aq
1
is a t parameter that refers to
very low values of scavenger power k[S] (i.e., F(S)!0). This g-value is a little lower than the
generally accepted value in Eq. (7), which is appropriate to dilute solutions where, typically,
k[S] = 10
7
sec
1
and F(S) c0.1.
The form of Eq. (15) assumes that G(e
aq
1
is the yield of
e
aq
that escapes from the track into the bulk solution at innite time. This is a reasonable
assumption under most experimental conditions where k
10
[S
1
]z10
6
sec
1
. On the other
hand, the data in Fig. 6 for lower scavenger power do suggest that the true yield that would
escape from a low LET track in pure water is less than 2.55 molecules (100 eV)
1
.
La Verne and Pimblott [19] and Pimblott and La Verne [43] rened Eq. (15) and
developed an analytical description of these eects of scavengers using the deterministic
diusion kinetic model outlined in Section 2. For a single scavenger, they showed that the
dependence of the amount of scavenging reaction on the concentration of S could be better
described by [22]:
GX
s
gX G
o
X gXFS 16
where X is the species of interest (e.g., e
aq
, H
2
, etc.) and F(S) is given by:
FS aS
1=2
aS=2=1 aS
1=2
aS=2 17
Here a =ak
s
where a, which is equal to 1/k in Eq. (15), is equivalent to a phenomenological
decay or formation time of the species X in the absence of scavenger and k
s
is the rate
constant of the scavenging reaction. Thus, the eects of dierent scavengers for a given
species X can be normalized using the relative values of k
s
. Applying this model to
scavenging data for e
aq
, LaVerne and Pimblott [19] and Pimblott and LaVerne [43] obtained
a good t to experimental data for the scavengers N
2
O, NO
3
, and CH
3
Cl with a = 0.905
nsec, g(e
aq
1
, and choosing G
o
(e
aq
1
.
The result is shown as the solid line in Fig. 6. They noted [19] that when no restriction was
placed on the value of G
o
(e
aq
), a best-t value of 4.3 molecules (100 eV)
1
was obtained for
this parameter.
Pimblott and LaVerne [43] then extended their model to cooperative scavenging and
obtained the following expression for cooperative scavenging of e
aq
:
Ge
aq
S
1
; S
2
2:55 2:25F9:1 10
10
s
1
1:2F5:5 10
10
fs
1
s
2
g
F5:5 10
10
s
1
18
where s
1
and s
2
are the scavenging powers of S
1
and S
2
, respectively, and the value of a for
reaction (R2) in Table 1 is 5.5 10
10
sec. The rst two terms on the right-hand side of
Eq. (18) represent the scavenging of e
aq
by the primary scavenger S
1
; the last two terms
represent the eect of the secondary scavenger S
2
for
.
OH through its interference with
the spur reaction e
aq
+
.
OH. The maximum yield of this reaction was estimated [43] to be
1
; a very similar value was obtained by Swiatla-Wojcik and Buxton
[9] in their deterministic modelling (see Table 1).
Time Dependence of G(e
aq
)
The time dependence of the yield of hydrated electrons during the chemical stage of water
radiolysis (ca. 10
12
to 10
6
sec) can be obtained from scavenging studies and by direct
observation using pulse radiolysis. In the former case, the scavenger dependence G(S) is
converted into the time dependence using the inverse Laplace transform of F(S) to F(t),
which is given by Eqs. (19) and (20):
Ft expkterfckt
1=2
for Eq: 15 19
Ft 2F
f
4:0kt=p
1=2
for Eq: 17 20
In Eq. (20), F
f
is the auxiliary function for the Fresnel integrals [44]. In practice, it is usual to
choose empirical scavenging functions F(S) that have analytical inverse Laplace transforms.
The rst pulse radiolysis experiments to measure G
o
(e
aq
) directly were made in the
1970s, with reported values of 4.0 F 0.2 molecules (100 eV)
1
at 30 psec [45] and 4.1 F 0.1
molecules (100 eV)
1
at >200 psec [46]. The latter value was subsequently revised to 4.6 F
1
at 100 psec [47], and later a yield of 4.8 F0.3 molecules (100 eV)
1
at 30 psec was reported by Sumiyoshi et al. [48]. The method of evaluating G(e
aq
) at these
short times is either to use dosimetry [45,46] and the molar absorption coecient of e
aq
, or to
compare the optical absorbance at short times with that observed at 10
7
10
6
sec and take
G(e
aq
1
at this time [48]. The causes of the discrepancies between
these pulse radiolysis values have been reviewed recently by Bartels et al. [49], who have also
made new measurements of the spur decay of e
aq
.
In their pulse radiolysis experiments, Bartels et al. [49] measured directly the decay
of e
aq
from 100 psec out to microseconds. By using the four exponential sum in Eq. (21) to
t the observed decay, they obtained a ratio G
o
(0)/G
inf
of 1.59, eectively equivalent to
G
o
(e
aq
)/g(e
aq
):
G
o
t=G
inf
1 0:090expt=139nsec 0:128expt=24:4nsec
0:255expt=3:51nsec 0:118expt=0:480nsec 21
Fromthe time dependence of the optical absorbance due to e
aq
, Bartels et al. [49] found that
if they assumed G
inf
=2.5 molecules (100 eV)
1
, then they calculated G(e
aq
) =2.7 molecules
(100 eV)
1
for a scavenging power of 10
7
sec
1
(see Fig. 6). Thus, these data are in accord
with G(e
aq
) in reaction (7) and with the rst term on the right-hand side of Eq. (15). On the
other hand, Bartels et al. [49] obtained G
o
(0) (i.e., G
o
(e
aq
) =4.0 F0.2 molecules (100 eV)
1
),
some 20% lower than the value of Schwarz [8]. Their predicted scavenging curve is
compared with that of Pimblott and LaVerne [43] in Fig. 6. Because of the scatter in the
experimental data, the t parameters of the calculated curves are not tightly dened. This is
especially true for G
o
(e
aq
) because the maximum scavenging power that can be used
experimentally is limited to ca. 10
10
sec
1
, corresponding to
f
100 psec in real time. A
reason put forward by Bartels et al. [49] to account for G(P
1
)>G(e
aq
) is that the electron may
react with the scavenger in its presolvation state e
pre
, as discussed in Section 3.1.

The experimentally determined value of G
o
(e
aq
) =4.0 F0.2 molecules (100 eV)
1
[49]
has implications for the stochastic and deterministic models of the radiolysis of water
because, as noted in Section 2, G
o
(e
aq
) at 1 psec is calculated to be 5.3 molecules (100 eV)
1
[10] and 4.9 molecules (100 eV)
1
[20]. On the other hand, for the deterministic model [9],
it has been shown [24] that G
o
(e
aq
1
is accommodated by
increasing the initial width of the assumed Gaussian distribution of e
aq
from 2.3 to 3.8 nm.
Another factor to be considered is the extent to which e
aq
decays in the time interval 1100
psec, which at present is largely inaccessible experimentally. The ratio calculated from Eq.
(21) at 100 psec (i.e., G(100 psec)/G
inf
) is 1.56, indicating that e
aq
decays by only 1.8%
between 10
12
and 10
10
sec. This is quite close to the decay of 2.1% predicted by the
stochastic simulations of Pimblott and LaVerne, assuming a Gaussian distribution of
thermalized electrons with r
o
=4 nm [20], but much smaller than the 11.6% decay obtained
by Frongillo et al. [10b] (see Section 2). The deterministic model calculations predict decays
of 8.0% and 3.1% for Gaussian distributions with r
o
= 2.3 nm [9] and 3.8 nm [24],
respectively. In the deterministic model, G
o
(e
aq
) and r
o
are adjustable parameters, whereas
the stochastic treatment automatically generates the value of G
o
(e
aq
) and the distribution of
thermalized electrons. If the results obtained by Bartels et al. [49] are correct, then the
stochastic calculations [10,20] need to be revisited.
To make a complete interpretation of the scavenging data in Fig. 6, one has to consider
the reactivity of the electron in the various states in which it can exist before it reaches its
fully solvated state [33] as discussed in Section 3.1. Static scavenging must also be taken into
account when e
aq
is formed within the reaction distance of the solute so that it reacts before it
can be observed [50]. Hence, it is not surprising that the data in Fig. 6 do not conformto the
unied curve for G(e
aq
) in Fig. 4. Therefore, in chemical applications involving concentrated
solutions, one should measure G(P
1
) in the system of interest. If this is not feasible, then it
should be recognized that the value calculated from scavenging functions based only on the
reactivity of e
aq
could be in error by as much as 10%.
3.3. G(
.
OH)
By comparison with G(e
aq
), relatively few independent measurements of G(
.
OH) have been
made. In contrast to e
aq
, only the relative change in G(
.
OH) with time has been reliably
measured by pulse radiolysis [51]. In practice, absolute values of G(
.
OH) have been obtained
from scavenger studies or by material balance (reaction (7)). Fig. 7 shows data for aerated
solutions of formate ion [52] and hexacyanoferrate(II) [53] taken fromFig. 1 of Ref. 54. The
data for formic acid, which were included by LaVerne and Pimblott [54], have been omitted
here because they were obtained at low pH where the primary yields are dierent (see Sec-
tion 3.4). The solid line shows the best t obtained using Eqs. (16) and (17) and the broken
line is the best t when the term a[S]/2 is omitted from Eq. (17). The respective sets of
parameters are a = 1.64 and 1.69 nsec, g(
.
OH) = 2.53 and 2.50 molecules (100 eV)
1
, and
G
o
(
.
OH) = 4.48 and 4.86 molecules (100 eV)
1
. These values dier signicantly from those
obtained by LaVerne and Pimblott [54], which were a = 0.258 nsec, g(
.
OH) = 2.66
molecules (100 eV)
1
, and G
o
(
.
OH) = 5.50 molecules (100 eV)
1
. The reason for the
dierence is that LaVerne and Pimblott [54] chose G
o
(
.
OH) = 5.50 molecules (100 eV)
1
.
When no constraints were placed on the tting parameters, G
o
(
.
OH) was found to be 4.4
molecules (100 eV)
1
[54], which is closer to those given above for the data in Fig. 7. Sub-
sequently, Pimblott and LaVerne [20] compared the results of their stochastic simulations
with the scavenging data. However, their simulations predicted G
o
(e
aq
) c 4.9 molecules
(100 eV)
1
and G
o
(
.
OH) c5.5 molecules (100 eV)
1
, respectively, which nowseemto be too
large when compared with the results and conclusions of Bartels et al. [49] (i.e., G
o
(e
aq
) c4.0
molecules (100 eV)
1
and G
o
(
.
OH) c5.1 molecules (100 eV)
1
).
The question of the magnitude of G
o
(
.
OH) has been addressed recently by Jay-Gerin
and Ferradini [55] who concluded that a value of 4.6F0.25 molecules (100 eV)
1
at 100 psec
is consistent with the scavenger data in Fig. 7 and with stochastic simulation results, which
give G
o
(
.
OH) equal to 5.8 molecules (100 eV)
1
at 1 psec and G(
.
OH) = 4.8 molecules (100
eV)
1
at 100 psec [10]. This represents a 17.2% decrease in G(
.
OH) over this period. The
eect of using G
o
(e
aq
) =4.1 instead of 4.78 molecules (100 eV)
1
in the deterministic model
[9,24] is to make G
o
(
.
OH) 4.9 molecules (100 eV)
1
instead of 5.5 molecules (100 eV)
1
. The
corresponding decreases in G(
.
OH) between 10
12
and 10
10
sec are 8.3% and 14.1%,
respectively.
In contrast to the data in Fig. 7, Sutton et al. [56], using pulse radiolysis, measured
G(Br
.
2
)e(Br
.
2
), where e is the molar absorption coecient, and found it to be independent
of the concentration of Br
over the range 2 10

3
to 1.0 mol dm
3
in O
2
-saturated solution
at neutral pH. It was necessary to use a low dose per pulse (26 Gy) to exclude interradical
combination during the growth of Br
.
2
. Under these conditions, the formation of Br
.
2
occurs via reactions (22)(24):
.
OH Br
! HOBr
.
22
HOBr
.
WOH
Br
.
23
Br
.
Br
WBr
.
2
24
Figure 7 Comparison of experimental and predicted values of G(P
2
) from hydroxyl radical
scavenging as a function of the scavenger power k
11
[S
2
]. S
2
= HCO
2
(n); FeCN
4
6
(E). The full
and broken lines are the best ts of Eqs. (16) and (17) without any restriction on the parameters (see
text). (From Ref. 54.)
To explain their results, Sutton et al. [56] suggested that spur reactions (R2) and (R8) in
Table 1 be replaced by reactions (25) and (26), which are equally ecient:
e
aq
Br
.
=Br
.
2
! Br
=2Br
25
Br
.
Br
.
! Br
2
26
Similarly, it was found that G(P
2
) is independent of [S
2
] for the
.
OH scavengers thiocyanate
ion [57] and iodide ion [58]. Clearly, there is good evidence that back reactions such as
reaction (25) can occur in the spur and thus modify G(P
2
).
G(
.
OH) in N
2
O-Saturated Solution
In applications of water radiolysis to free radical chemistry, it is particularly convenient to
use aqueous solutions saturated with N
2
O, where e
aq
is converted to
.
OH via reactions (27)
and (28) [59]:
e
aq
N
2
O ! O
.
N
2
; k
27
9:1 10
9
dm
3
mol
1
sec
1
27
O
.
H
2
O W
.
OH OH
; k
28
1:7 10
6
dm
3
mol
1
sec
1
28
k
28
1:2 10
10
dm
3
mol
1
sec
1
Under normal conditions of room temperature and atmospherical pressure, the saturation
concentration of N
2
O is ca. 2.5 10
2
mol dm
3
and its scavenging power is ca. 2.3 10
8
sec
1
. Thus, one has to consider that reactions (27) and (28) generate extra
.
OH in the spurs
because k
28
[H
2
O] =9.4 10
7
sec
1
. This problemwas addressed by Schuler et al. [60], who
showed that the scavengeable yield of
.
OH is described by the empirical equation, Eq. (29),
which is analogous to Eq. (15):
G
.
OH 5:2
3:0kS=k
1=2
1 kSk
1=2
molecule 100eV
1
29
where k = 4.7 10
8
sec
1
and k[S] is the scavenging power of the solute reacting with
.
OH
(i.e., k
11
[S
2
]). Thus, the
.
OHthat replaces e
aq
in the spurs through reactions (27) and (28) also
participates in spur reactions. Values of G(
.
OH) calculated from Eq. (29) are plotted vs.
scavenging power in Fig. 8.
3.4. pH Dependence of the Primary Yields g(X)
This is illustrated in Fig. 9 for low LET radiation. At pH >3, the g-values are eectively
constant; at pH<3, the extent of reaction (R1) increases through scavenging of e
aq
in the
spurs. The observed increase in g(e
aq
) + g(H
.
) is probably due to the diusion coecient
of H
.
(D
H
= (7.0 F 1.5) 10
9
m
2
sec
1
[61]) being larger than that of e
aq
(D
e
= (4.90 F
0.02) 10
9
m
2
sec
1
[62]), and reaction (R7) (k
R7
=1.5 10
10
dm
3
mol
1
sec
1
[63]) being
slower than reaction (R2) (k
R2
=3.010
10
dm
3
mol
1
sec
1
[59]), so that conversion of e
aq
to
H
.
in the spurs favors diusive escape into the bulk liquid. The change in the individual
values of g(e
aq
) and g(H
.
) with pH has been measured [6] with chloroacetic as the
scavenger, as described in Section 1. The data are shown in Fig. 10:
e
aq
ClCH
2
CO
2
H ! Cl

.
CH
2
CO
2
H 4
H
.
ClCH
2
CO
2
H ! H
2

.
CHClCO
2
H 5
The values of g(
.
OH) and g(H
2
O
2
) also increase at pH<3, as shown in Fig. 9. An
increase in the yield of oxidizing equivalents is expected, of course, to maintain the balance
with the increase in g(e
aq
)+g(H
.
), but the increase in g(H
2
O
2
) does suggest that reaction (R8)
becomes more important when reaction (R7) replaces reaction (R2) at low pH.
The conversion of H
.
to e
aq
takes place at high pH through reaction (30):

H
.
OH
! e
aq
; k
30
2:2 10
7
dm
3
mol
1
sec
1
59 30
Although reaction (30) is too slowto interfere signicantly with spur processes up to pH14,
it may compete with the reaction of H
.
with other solutes in the bulk solution under these
conditions and thus increase G(e
aq
).
Figure 8 Values calculated from Eq. (29) of G(
.
OH) vs. scavenging power k
11
[S
2
] in N
2
O-saturated
solution.
Figure 9 Dependence of the primary yields g(X) on pH. (From Ref. 52.)
4. PROPERTIES OF THE PRIMARY RADICALS
The properties of the primary radicals produced by the radiolysis of water are collected in
Table 2.
4.1. The Hydrated Electron
Although its precise structure has not yet been settled, the hydrated electron may be
visualized as an excess electron surrounded by a small number of oriented water molecules
and behaving in some ways like a singly charged anion of about the same size as the iodide
ion. Its intense absorption band in the visible region of the spectrummakes it a simple matter
to measure its reaction rate constants using pulse radiolysis combined with kinetic
spectrophotometry. Rate constants for several hundred dierent reactions have been
obtained in this way, making e
aq
kinetically one of the most studied chemical entities.
As expected from its standard reduction potential of 2.9 V (Table 2), e
aq
reacts
rapidly with many species having more positive reduction potentials. Its mode of reaction
can be represented as the one-electron transfer process (reaction (31):
e
aq
S
n
! S
n1
31
where n is the charge on the solute. In some cases, the electron adduct S
n1
immediately
dissociates (e.g., as in reactions (4), (14), and (27) shown above). Values of k
31
range fromca.
10
1
dm
3
mol
1
sec
1
up to the diusion-controlled limit of ca. 10
10
dm
3
mol
1
sec
1
.
However, the activation energies are invariably small and generally fall in the range 630 kJ
mol
1
, with the majority around 15 kJ mol
1
. The latter observation led Hart and Anbar
[67] to suggest that reaction (31) has an activation energy associated with reorientation of
the solvent shell to facilitate transfer of the electron, and that this reorientation energy is the
same as that required for e
aq
to diuse in water. The corollary to this argument is that the
Figure 10 Dependence of g(e
aq
) and g(H
.
) on pH. (From Ref. 6.)
entropy of activation energy is the dominant kinetic parameter, and this can be understood
in terms of the availability of a suitable vacant orbital on the acceptor molecule S
n
into which
the electron can transfer from its solvent shell. Molecules such as water, simple alcohols,
ethers, and amines have no low-lying vacant orbitals, and this explains why solvated
electrons can be observed in these liquids.
The kinetics of the reactions of e
aq
can be rationalized as follows. The general
expression for a time-independent rate constant in solution is [68]:
1=k
obs
1=k
diff
1=k
read
32
where k
obs
, k
di
, and k
react
are the observed, diusion-controlled, and activation-controlled
rate constants, respectively. When the rate of a reaction is diusion-controlled (k
react
k
di
),
it is impossible to obtain details of the chemical step in the overall process of encounter and
reaction, but such information is revealed by raising the temperature so that the diusion
step becomes much faster than the chemical step. In this way, it has been shown [69] that
some reactions of e
aq
(e.g., with NO
2
, NO
3
, SeO
2
4
, and phenol) are reversible in the chemical
step, which accounts for the abnormally low activation energy that was reported for NO
2
[70]. In fact, the activation energy becomes negative as the temperature is raised above
100jC, as shown in Fig. 11.
These reactions can be described by the following general scheme for transfer of an
electron from a donor D to an acceptor A [71]:
D AWD=AWD=A* WD
=A
* ! D
=A
! product 33
where [D/A]* and [D
+
/A
]* represent the reorganized precursor and successor complexes

involved in the electron transfer step. This scheme predicts that the observed activation
energy will switch from a positive to a negative value if the relaxation of [D/A]* back to [D/
A] has a larger temperature dependence than the reorganization of [D/A] to [D/A]*. In the
Table 2 Selected Properties of the Radicals e
aq
, H
.
,
.
OH, and O
.
in aqueous solution
Property e
aq
H
. .
OH O
.
Absorption maximum (nm) 720 <200
f
225 240
Molar absorption
coecient (m
2
mol
1
)
200 (720 nm)
[65]
95 (200 nm)
[66]
50 (250 nm)
[63]
24 (240 nm)
[64]
Diusion coecient
(10
9
m
2
sec
1
)
4.9 [62] 7 [61] 2.2
Equivalent conductivity
(S cm
2
mol
1
)
190
Mobility (10
3
cm
2
V
1
sec
1
)
1.9
Reduction potential (V) 2.9
a
2.3
b
2.7
c
, 1.9
d
1.7
e
pK
a
9.6
f
11.9
g
The data are taken from Table 1 in Ref. 59 unless stated otherwise.
a
(H
2
O+e
! e
aq
).
b
(H
2
O+e
+H
+
!
.
H
aq
).
c
(
.
OH+e
+H
+
! H
2
O).
d
(
.
OH+e
!OH
).
e
(O
.
+e
+H
+
! OH
).
f
(H
.
+H
2
O!H
3
O
+
+e
aq
).
g
(
.
OH+H
2
O!H
3
O
+
+O
.
).
case of NO
2
, the calculated line in Fig. 11 was obtained with values of E
act
=24.9 and 7.2 kJ
mol
1
, respectively, for these two steps [69].
The hydrated electron behaves as a nucleophile in its reactions with organic molecules
and its reactivity is greatly enhanced by electron-withdrawing substituents attached to
aromatic rings or adjacent to double bonds. Some of the features of the reactivity of e
aq
are
illustrated by the data in Table 3.
4.2. The Hydrogen Atom
The hydrogen atom is the conjugate acid of e
aq
and can be thought of as a weak acid with a
formal pK
a
of 9.7, obtained from the rate constants of reactions (30) and (34) [59]:
e
aq
H
2
O ! H
.
OH
; k
34
19dm
3
mol
1
sec
1
34
It is not an important species in the radiation chemistry of neutral and alkaline solution
(reaction (7)), but it is the major reducing species in acidic solution (see Fig. 10). Having
a reduction potential of 2.3 V (Table 2), H
.
is a slightly less powerful reducing agent than
e
aq
, but its chemistry is often quite dierent. Agood example of this is provided by reactions
(4) and (5). H
.
readily reduces inorganic ions having more positive reduction potentials than
itself, but often at slower rates than e
aq
. In some cases, in strongly acidic solution, it
eectively acts as an oxidant, forming a hydride intermediate, which reacts with H
+
to
eliminate H
2
and leave the oxidized form of the solute as in reactions (35) and (36):
H
.
Fe
2
! Fe
3
H
!
H
Fe
3
H
2
35
H
.
I
! HI
!
I
HI
2
2
!
H
I
2
.
H
2
36
Figure 11 Arrhenius plot of k(e
aq
NO
2
). The solid circles show the values of k
react
obtained from
Eq. (32). The solid line shows the t of reaction (33). Note the inuence of k
di
on k
obs
. (From Ref.
69.)
H
.
generally reacts with organic compounds by abstracting a hydrogen atom from
saturated molecules and by adding to centers of unsaturation, for example:
H
.
CH
3
OH !
.
CH
2
OH H
2
37
H
.
CH
2
jCH
2
!
.
CH
2
CH
3
38
Because H
.
absorbs only weakly in the ultraviolet region of the spectrum(Table 2) and
g(
.
H) is relatively small in neutral solution, its optical signal cannot generally be used for
making direct measurements of its rate of reaction with solutes, but in suitable cases, the
required data can be obtained by observing the rate of growth of an absorbing product. Rate
constants have also been determined directly by observation in pulse radiolysis experiments
of the ESRsignal of the hydrogen atom, which is possible because of its enhancement by spin
polarization eects [72,73].
More generally, the method of competition kinetics is used to determine H-atom rate
constants. The hexacyanoferrate(III) ion is a suitable solute because reaction (39) can be
followed fromthe decrease in absorbance at 420 nmdue to FeCN
3
6
(e
420
=104 m
2
mol
1
).
When a second solute is present so that reaction (40) competes with reaction (39), G(Fe
CN
3
6
) is given by Eq. (41):
H
.
FeCN
3
6
! FeCN
4
6
H
39
H
.
S ! P 40
1
GFeCN
3
6

1
GH
.
1
k
40
S
k
39
FeCN
3
6

!
41
Table 3 Rate Constants for Selected Reactions of e
aq
at Room Temperature
Solute (inorganic) k (dm
3
mol
1
sec
1
) Solute (organic) k (dm
3
mol
1
sec
1
)
Ag
+
3.910
10
C
6
H
6
1.110
7
H
3
O
+
2.310
10
C
6
H
5
Cl 6.410
8
NH
4
1.510
6
C
6
H
5
I 1.210
10
Cd
2+
5.310
10
C
6
H
5
NO
2
3.710
10
Co(NH
3
3
8.710
10
C
6
H
5
NH
2
2.810
7
Fe
3
6.010
10
C
5
H
5
N (pyridine) 1.010
9
ClO
4
<110
6
MV
2+ a
7.210
10
MnO
4
2.610
10
CH
4
<110
7
CrO
2
4
1.810
10
CH
3
CN 3.710
7
FeCN
3
6
3.110
9
CH
3
I 1.610
10
FeCN
4
6
<710
4
CH
3
OH <110
4
CO
2
7.710
9
CH
2
I
2
3.410
10
H
2
O 19 C(NO
2
)
4
5.310
10
H
2
O
2
1.110
10
C
2
H
2
2.010
7
N
2
O 9.110
9
CH
2
jCH
2
<310
5
O
2
1.910
10
CH
2
jCCl
2
2.310
10
a
MV
2+
=1,1V-dimethyl-4,4V-bipyridinium ion.
Source: Ref. 59.
4.3. The Hydroxyl Radical
The hydroxyl radical is a powerful oxidant, having a reduction potential of 2.7 V in acidic
solution. In neutral solution, where the free energy of neutralization of OH
by H
3
O
+
is not
available, the reduction potential decreases to 1.9 V (Table 2). Several inorganic anions and
low-valency transition metal ions readily undergo one-electron oxidation by reaction with
.
OH, which is often represented as a simple electron transfer:
.
OH S
n
! S
n1
OH
42
where n is the ionic charge. However, although the stoichiometry is described by reaction
(42), there are many examples which show that the reaction actually proceeds via the
formation of an adduct, followed by an inner-sphere electron transfer. In the case of halide
and pseudo-halide ions, X
(X=Cl, Br, I, and SCN), the intermediate species HOX

.
have
been observed by pulse radiolysis (cf. reaction (22)). Similarly, the oxidation of metal ions
has been shown to occur as in reaction (43):
.
OH M
n
! M
n
OH ! M
n1
OH
43
for M
n+
= Tl
+
, Ag
+
, Cu
2+
, Sn
2+
, Fe
2+
, Mn
2+
, and Cr
3+
. It has been proposed [74] that
.
OH is generally unlikely to react by accepting an electron fromthe donor by a simple outer-
sphere transfer because of the large solvent reorganization energy involved in the formation
of the hydroxide ion. This idea is certainly supported by the experimental results relating to
reactions (42) and (43).
Although
.
OH reacts at near-diusion-controlled rates with inorganic anions [59],
there seems to be an upper limit of ca. 3 10
8
dm
3
mol
1
sec
1
in the case of simple hydrated
metal ions, irrespective of the reduction potential of M
n+
. Also, there is no correlation
between the measured values of k
43
and the rates of exchange of water molecules in the rst
hydration shell of M
n+
, which rules out direct substitution of
.
OH for H
2
O as a general
mechanism. Other mechanisms that have been proposed are (i) abstraction of H from a
coordinated H
2
O [75,76], and (ii)
.
OH entering the rst hydration shell to increase the
coordination number by one, followed by inner-sphere electron transfer [77,78]. Data
reported [78] for M
n+
= Cr
3+
, for which the half-life for water exchange is of the order of
days, are consistent with mechanism (ii):
.
OH Cr
III
WCr
III
.
OH ! Cr
IV
OH
44
In alkaline solution at pH >10,
.
OH reacts rapidly with hydroxide ion to form O
.
,
with k
45
= 1.2 10
10
dm
3
mol
1
sec
1
and k
45
= 9.3 10
7
sec
1
[59] so that equilibrium
(reaction (45)) is established when k
11
[S
2
]<10
7
sec
1
for
.
OH reactions:
.
OH OH
WO
.
H
2
O 45
It is important to note that, as expressed here, K
45
= 130 dm
3
mol
1
is a concentration
equilibrium constant. Thus, when equilibrium is established,
.
OH makes up 8% of the total
concentration of hydroxyl radicals in 0.1 mol dm
3
OH
solution, and 0.8% in 1 mol dm

3
OH
solution. Consequently, corrections for the presence of

.
OH will generally be neces-
sary when measuring rates of O
.
reactions when the latter are signicantly slower than
those of
.
OH. For the reaction scheme (reactions (45) (46) (47)):
.
OH S ! P 46
O
.
S ! P 47
the observed rate constant is given by Eq. (48):
k
obs

k
46
k
47
K
45
OH
1
K
45
OH
48
so that by varying [OH
], one can evaluate k

46
and k
47
unambiguously, provided that the
reactivity of the solute S does not change in the pH range of interest.
O
.
is generally less reactive than
.
OH with inorganic anions, and the rate is immea-
surably slowwith Br
, CO
2
3
, and FeCN
4
6
, although these ions all react rapidly with
.
OH.
This dierence in reactivity was used to establish the pK
a
of
.
OHas 11.9 (Table 2). O
.
reacts
rapidly with O
2
as in reaction (49), whereas
.
OH is unreactive:
O
.
O
2
WO
.
3
49
For this reaction, k
49
=3.5 10
9
dm
3
mol
1
sec
1
and K
49
=1.8 10
6
dm
3
mol
1
at 20jC
[79]. These kinetic properties and the characteristic absorption spectrumof O
.
3
(k
max
=430
nm, e
430
= 190 m
2
mol
1
[64]) make O
2
a suitable reference solute for the measurement of
rate constants of O
.
reactions by the method of competition kinetics [79].
In their reactions with organic compounds,
.
OH is electrophilic and O
.
is nucleo-
philic. Thus,
.
OH behaves like H
.
, readily adding to double bonds and aromatic rings,
whereas O
.
does not. Both forms of the radical abstract an H atom from CUH bonds and
this can result in dierent products in neutral and alkaline solutions. This is exemplied by
toluene, which reacts with
.
OH and O
.
as in reactions (50) and (51), respectively:
.
OH C
6
H
5
CH
3
! HOC
6
H
5
CH
3
.
50
O
.
C
6
H
5
CH
3
!
.
CH
2
C
6
H
5
OH
51
with k
50
= 5.1 10
9
dm
3
mol
1
sec
1
[80] and k
51
= 2.110
9
dm
3
mol
1
sec
1
[81].
Although
.
OHbehaves mechanistically like H
.
in its reactions with organic molecules,
it is less selective and more reactive than H
.
in H-abstraction reactions because the formation
of the HUOH bond is 57 kJ mol
1
more exothermic than that of HUH. Examples of the
reactivities of H
.
,
.
OH, and O
.
are listed in Table 4.
Measurements of the rates of reactions such as reaction (50) over an extended tem-
perature range reveal that k
obs
increases by less than threefold up to 150jC and then de-
Table 4 Rate Constants for Selected Reactions of
.
OH, H
.
, and O
.
at Room Temperature
k (10
7
dm
3
mol
1
sec
1
)
Solute Reaction type
.
OH H
.
O
. a
CH
2
=CHCONH
2
Addition 590 3100 65
C
6
H
5
CH
3
Addition 510 260 210
C
6
H
5
CO
2
Addition 590 85
f
4
CH
3
OH Abstraction 97 0.26 75
CH
3
CH
2
CH
2
OH Abstraction 280 2.4 150
(CH
3
)
2
CHOH Abstraction 190 7.4 120
HCO
2
Abstraction 320 21 140
a
Abstraction reactions.
Source: Ref. 59.
creases slightly up to 200jC as shown in Fig. 12 for C
6
H
6
, C
6
H
5
Cl, C
6
H
5
NO
2
, C
6
H
5
CO
2
H,
and C
6
H
5
CO
2
[82].
The variations of k
obs
with temperature are all very similar, but the absolute values of
k
obs
depend on the substituent on the aromatic ring. To explain these results, Ashton et al.
[82] proposed the following mechanismwhereby
.
OHadds reversibly to forma p-complex as
a precursor of the nal r-bonded hydroxycyclohexadienyl radical:
.
OH C
6
H
5
X WHOC
6
H
5
.
p
52
HOC
6
H
5
p
.
! HOC
6
H
5
.
r
53
Application of the steady-state approximation to HOC
6
H
5
.
r
in this reaction scheme
leads to:
k
obs
k
52
k
53
=k
52
k
53
54
On the assumption that reaction (52) is diusion-controlled, Ashton et al. [82] found that
rearrangement of HOC
6
H
5
.
p
to HOC
6
H
5
.
r
requires virtually no activation energy, whereas
dissociation of HOC
6
H
5
.
r
in reaction (52) has an activation energy of ca. 20 kJ mol
1
. The
dierences in the absolute values of k
obs
are reected largely in the values of k
53
, suggesting
that the electronic eects of the substituents govern the rate of rearrangement. These
parameters are summarized in Table 5.
4.4. The Perhydroxyl Radical HO
2
.
Although HO
.
2
and its conjugate base O
.
2
are only signicant primary radicals for high LET
radiation, they are important secondary radicals in oxygenated solution where they are
formed in reactions (55)(58):
e
aq
O
2
! O
.
2
55
H
.
O
2
! HO
.
2
56
Figure 12 Arrhenius plots for the reaction of
.
OH with some aromatic compounds. (From Ref.
82.)
HO
.
2
W O
.
2
H
57
The pK
a
of HO
.
2
is 4.8 [83], and both O
.
2
and HO
.
2
have reducing and oxidizing properties.
The reduction potentials are 0.33 Vfor the O
2
/O
2
.
couple with respect to a standard state
of 1 atm pressure of O
2
[83] and 0.05 V for the O
2
, H
+
/HO
.
2
couple [84] so that O
.
2
is the
better reductant. Conversely, HO
.
2
is the better oxidant, the reduction potentials being 1.45
V for the (H
+
, HO
.
2
/H
2
O
2
) couple and 1.03 V for the (O
.
2
, H
+
/HO
2
) couple [84].
HO
.
2
and O
.
2
have characteristic absorption spectra with e
max
=140 m
2
mol
1
at 225
nm [83] and e
max
= 189 m
2
mol
1
at 245 nm [85], respectively, which are suciently intense
to permit their reactions to be followed by direct observation in pulse radiolysis experiments.
Both radicals are relatively unreactive with organic molecules [83], abstracting only weakly
bonded hydrogen atoms in, for example, ascorbic acid, cysteine, and hydroquinone. O
.
2
undergoes reversible electron transfer in its reaction with quinones (Q), which was used to
establish its reduction potential [86]:
O
.
2
Q WO
2
Q
.
58
Acareful study of the bimolecular decay of HO
.
2
/O
.
2
in the absence of metal ions has shown
[84] that the reactions involved are reactions (59) and (60):
HO
.
2
HO
.
2
! H
2
O
2
O
2
59
HO
.
2
O
.
2
!
H
H
2
O
2
O
2
60
There is no evidence that reaction (61) takes place at a measurable rate under ambient
conditions, but it is rapid in the presence of aquo-complexes and some organo-complexes of
copper ions via reactions (62) and (63):
O
.
2
O
.
2
2H
! H
2
O
2
O
2
61
O
.
2
Cu
II
! Cu
I
O
2
62
O
.
2
Cu
I
2H
! H
2
O
2
Cu
II
63
Reaction (63) is an example of O
.
2
acting as an oxidant and it probably proceeds via an
inner-sphere electron transfer mechanismin which incompletely coordinated Cu
I
binds O
.
2
prior to electron transfer [87]. HO
.
2
and O
.
2
also react readily with a number of other
transition metal ions, either by electron transfer or through the formation of a complex [83],
for example:
O
2
.
Mn
2
! MnO
2
64
HO
.
2
Fe
2
! Fe
3
.
HO
2
!
H
Fe
3
H
2
O
2
65
Table 5 Rate Constants and Activation Energies for Reactions (52) and (53)
k (10
9
dm
3
mol
1
sec
1
) E
act
(kJ mol
1
)
X Reaction (52) Reaction (53) Reaction (52) Reaction (53)
H 6.5 14 18 0.5
Cl 4.0 12 22 0.5
NO
2
4.0 4 20 1.3
CO
2
3.8 13 21 1.0
CO
2
H 4.0 8 23 1.0
Source: Ref. 82.
Reactions (66) and (67) provide a very convenient way of converting
.
OH to O
.
2
:
.
OH HCO
2
! CO
.
2
H
2
O 66
CO
.
2
O
2
! O
.
2
CO
2
67
Thus, all the primary water radicals can be converted into HO
.
2
/O
.
2
in reactions (55), (56),
(66), and (67).
5. GENERATION OF SECONDARY RADICALS
As we have seen in Sections 1 and 4, the principal primary products of the radiolysis of water
are powerful oxidizing and reducing radicals in approximately equal yields. For water
radiolysis to be a useful tool in general chemistry, it is desirable to convert the primary
radicals to a single kind of secondary radical to achieve either totally oxidizing or reducing
conditions. Moreover, there is the possibility of designing the system to have the required
redox properties by suitable selection of the secondary radicals. Some useful systems that
meet these requirements are described below.
5.1. Oxidizing Conditions
As noted in Section 3.3, reactions (27) and (28) provide a very convenient way of converting
e
aq
to
.
OH. Because reaction (68) is relatively slow, approximately 10% of the radicals in
N
2
O-saturated neutral solution remain as reducing radicals in the formof H
.
, but this small
fraction can be allowed for or even be neglected in chemical applications:
H
.
N
2
O !
.
OH N
2
; k
68
2:1 10
6
dm
3
mol
1
sec
1
68
At pH>11, where reaction (30) becomes increasingly important, G(
.
OH) can increase by up
to 0.6 molecule (100 eV)
1
(i.e., g(H
.
), whereas at pH<3, G(
.
OH) becomes smaller because
reaction (3) competes with reaction (27). One should not forget that the product of reaction
(27) is O
.
rather than
.
OH[88,89]. Thus, if a solute that reacts with O
.
in competition with
its protonation in reaction (28) is present, then the reaction products may not be the same in
N
2
O-saturated solutions containing hydroxyl radical scavengers in high and low concen-
trations because O
.
can react dierently from
.
OH (see Section 4.3).
More selective oxidizing conditions can be achieved by converting
.
OH into another
inorganic radical (e.g., Br
.
2
, I
.
2
, SCN
.
2
, CO
.
3
, N
.
3
, etc.), thereby tuning the reduction
potential (see Table 6). One of the most powerful oxidizing radicals is SO
.
4
, which is
produced in reaction (69):
e
aq
S
2
O
2
8
! SO
.
4
SO
2
4
69
Because of its high reduction potential of 2.43 V (see Table 6), it can be used to generate
other strongly oxidizing radicals such as C1
.
and NO
.
3
through electron transfer reactions
with C1
and NO
3
, respectively [27].
Secondary inorganic radicals are particularly useful for studying redox changes in
metalloproteins and organometallic complexes because these radicals are more likely to
react at the metal center by electron transfer, whereas
.
OH will also attack the organic
moiety and, by abstracting H, create a reducing radical there.
5.2. Reducing Conditions
Although it is possible to convert
.
OHto e
aq
through reactions (70) and (30), the slowness of
these reactions means that conditions of 100 atm of hydrogen and high pH are required.
Nevertheless, these have been realized in experiments crucial to the measurement of spur
reactions (R5) and (R6) in Table 1 [91,92]:
.
OH H
2
! H
.
H
2
O; k
70
4:2 10
7
dm
3
mol
1
sec
1
59 70
A much more convenient method of obtaining totally reducing conditions is to convert all
the primary radicals to the same secondary reducing radical by adding the appropriate
organic solute to N
2
O-saturated water. A prime example of this is the generation of CO
.
2
through reactions (66) and (71):
H
.
HCO
2
! CO
.
2
H
2
; k
71
2:1 10
8
dm
3
mol
1
sec
1
59 71
Alternatively, N
2
O can be replaced by CO
2
so that CO
.
2
is produced in reaction (72):
e
aq
CO
2
! CO
.
2
; k
72
7:7 10
9
dm
3
mol
1
sec
1
59 72
Simple alcohols are often used as the source of the secondary radicals because they also react
rapidly with both
.
OH and H
.
(e.g., 2-propanol in reactions (73) and (74)):
.
OH CH
3
2
CHOH ! CH
3
2
.
COH H
2
O 73
H
.
CH
3
2
CHOH ! CH
3
2
.
COH H
2
74
It is the hydrogen atom on the a-carbon that is most readily abstracted, as indicated in
reactions (73) and (74). However,
.
OH does abstract H from other positions so that a
mixture of radicals is produced where only one is desired. The distributions of radicals
generated from a number of simple alcohols are given in Table 7.
Radicals derived from simple alcohols have a dissociable proton on the hydroxyl
group, for example:
CH
3
2
.
COH WCH
3
2
.
CO
; pK
a
12:03 94 75
Thus, one should bear in mind that the basic form of the radical will be generated when
pH>pK
a
and it is usually more strongly reducing than the acidic form. The values of pK
a
Table 6 Reduction Potentials of Some Inorganic Radicals
Redox couple E
o
(V) Redox couple E
o
(V)
Cl
.
/Cl
2.41 CO
.
3
/CO
2
3
1.5
Cl
.
2
/2 Cl
2.09 N
.
3
/N
3
1.33
Br
.
/Br
1.92 NO
.
2
/NO
2
1.04
Br
.
2
/2 Br
1.62 NO
.
3
/NO
3
2.5
I
.
/I
1.33 SO
.
3
/SO
2
3
0.63
I
.
2
/2 I
1.03 SO
.
4
/SO
2
4
2.43
SCN
.
/SCN
1.63 CN
.
/CN
2.59
SCN
.
2
/2SCN
1.32 OCN
.
/OCN
2.66
Source: Ref. 90.
and reduction potential for the more commonly used organic radicals are summarized in
Table 8.
CO
.
2
is a useful reducing radical because of its low pK
a
, which means that it can be
used in acidic solutions where e
aq
would react predominantly with H
+
. However, where it
is required to use e
aq
as the reductant, it is common practice to add 2-methyl-2-propanol
(tert-butanol) as the scavenger for
.
OH to convert it into the relatively unreactive radical
.
CH
2
(CH
3
)
2
COH:
.
OH CH
3
3
COH !
.
CH
2
CH
3
2
COH H
2
;
76
k
76
6:0 10
8
dm
3
mol
1
sec
1
59
In this way, the powerful reducing properties of e
aq
can be exploited to generate hyper-
reduced states of metal ions, for example:
e
aq
Cd
2
! Cd
77
The monovalent ions Cd
+
, Co
+
, Ni
+
, and Zn
+
are themselves quite strong reductants
and, being positively charged, can be used to reduce metalloproteins at sites where there
is a local negative charge that makes them less accessible to e
aq
[98].
Table 7 Percentage Abstraction of H-Atom by
.
OH from Various Positions
in Simple Alcohols
Alcohol a-CUH Other CUH OH
CH
3
OH 93.0 7.0
CH
3
CH
2
OH 84.3 13.2 2.5
CH
3
(CH
2
)
2
OH 53.4 46.0 <0.5
(CH
3
)
2
CHOH 85.5 13.3 1.2
CH
3
(CH
2
)
3
OH 41.0 58.5 <0.5
(CH
3
)
3
COH 95.7 4.3
(CH
2
OH)
2
100 <0.1
CH
3
CH(OH)CH
2
OH 79.2 20.7 <0.1
CH
3
CH(OH)CH(OH)CH
3
71.0 29.0 <0.1
Source: Ref. 93.
Table 8 Values of pK
a
and E
o
for Commonly Used Reducing Radicals
Obtained by Reaction of
.
OH with Simple Alcohols (see Table 7) and
Formate Ion
Radical pK
a
[94]
E
o
(RO, H
+
/ROH
.
)
(V) [95]
E
o
(RO/RO
.
)
(V) [95]
.
CH
2
OH 10.71 1.18 1.81
CH
3
.
CHOH 11.51 1.25 1.93
(CH
3
)
2
.
COH 12.03 1.39 2.10
.
CH
2
C(CH
3
)
2
OH 0.1 [96]
CO
.
2
0.2 [97] 1.90
6. APPLICATIONS IN GENERAL CHEMISTRY
The great advantage of radiolysis over other methods of producing free radicals is that only
the solvent absorbs the ionizing radiation in most chemical applications. Moreover, it is
clear from the foregoing information that the radiolysis of water provides a powerful
method of generating one-electron redox agents that can be nely tuned in terms of
reduction potential and electric charge. The use of pulse radiolysis in particular has resulted
in a great wealth of information being obtained on the kinetics and mechanisms of the
reactions of free radicals, and of metal ions in unusual oxidation states, in aqueous solution.
The chapters, each written by experts, in Radiation ChemistryPresent Status and Future
Trends [99] provide excellent descriptions of the diverse nature and applications of this eld
of study.
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13
Photochemistry and Radiation Chemistry
of Liquid Alkanes: Formation and Decay
of Low-Energy Excited States
L. Wojnarovits
Hungarian Academy of Sciences, Budapest, Hungary
1. INTRODUCTION
The radiation chemistry of alkanes was reviewed several times in the past. The books of
Topchiev [1] and Foldiak (editor) [2] deal mainly with the yield and distribution of nal
products. In the book edited by Gaumann and Hoigne [3] the yields of radical intermediates,
LET eects (linear energy transfer, energy lost when the particle passes unit length) reaction
mechanisms, etc. are discussed. Hydrocarbon chemistry dominates the book edited by
Ausloos [4]. Freeman [5] and, more recently, Hummel [6] explained ionizing-radiation-in-
duced chemical changes in alkanes based on the radiation chemical theories available at the
time of writing of their review papers. The most recent review published by Shkrob et al. [7]
concentrates on the liquid phase ion chemistry detailing the dierent views on the high-
mobility cations observed inseveral liquidcycloalkanes; they also discuss some aspects of the
excited-state chemistry. The formation and decay of excited alkane molecules was reviewed
in a recent book chapter of Mayer and Szadkowska-Nicze [8]. In addition to these special
books, book chapters or review articles on hydrocarbon radiolysis, or more specically on
alkane radiolysis, general radiation chemistry books also provide great attention to the
radiolysis of alkanes [913].
This chapter is concerned mainly with the chemistry of excited molecules in photon
and high-energy ionizing-radiation-induced processes of alkanes. Our knowledge on the
higher-energy excited states is rather limited, so the results on the reactions of lower energy
excited molecules are reviewed. We will compare the processes taking place in radiolysis
and photolysis and try to give more chemistry than reported in the previous reviews. Most
of the work done in this eld was published in the 1980s; however, as can be seen from the
reference list, more recent papers also appeared, which are incorporated in the review.
2. PHOTOCHEMISTRY OF LIQUID ALKANES
The electron excitation of molecules in nearly all classes of organic compounds can be
performed by visible or ultraviolet light (k
ex
>190 nm,<6.5 eV). There are a few ex-
ceptions, e.g., the alkanes, where excitation requires higher energies in the so-called
vacuum UV (VUV) region. The photon irradiation of alkanes is generally done in the
100- to 180-nm wavelength range; this range corresponds to a photon energy range of 712
eV. From the energy dependence and by comparing the data obtained in radiolysis and
photolysis, valuable information can be obtained concerning the activated intermediates
leading to the formation of stable end products in radiolysis.
Most publications dealing with the photodecomposition of alkanes discuss the
processes in the gas phase; several comprehensive works have already been published in
this eld [1417]. In the present work, we summarize the results of liquid phase photolytic
studies and compare them with those obtained in radiolysis. An early review on liquid
alkane photochemistry was published in Ref. 18, a brief overview of the eld was given in
Ref. 19.
2.1. Absorption and Emission Spectra of Alkanes, Ionization
in the Liquid Phase
The VUV absorption spectra of alkanes are rather featureless, usually without marked
peaks (as shown in Fig. 1 for n-hexane) in contrast to the spectra of aromatics or to the
spectra of compounds containing heteroatoms. Earlier works usually assumed that at low
energies in alkanes the excitation results in j!j*-type valence-electron transitions, but
later works concluded that the excitations, at least partly, result in Rydberg states [2023].
Figure 1 Absorption [20,21] and emission [25] spectra of n-hexane.
Rydberg-type orbitals are extended in space and resemble atomic orbitals, whereas the
valence excitations do not lead to signicant spatial extension. Consequently, the Rydberg
states are, in contrast to the valence-electron excitations, sensitive to external perturba-
tions coming from changes of pressure or phase (liquidgas). The probability of formation
of Rydberg orbitals in condensed phases is less than in gases, although many experimental
results indicate their existence, e.g., energy transfer from higher excited states (Sec. 3.2).
During irradiation of many alkanes with VUV photons, with visible or infrared
photons causing double or multiphoton excitation, or ionizing radiation, weak uores-
cence was rst observed at the end of the sixties with quantum yields of U
f
c10
5
to 10
2
[2426] (Table 1). The uorescence spectrum is a broad, structureless band around 170
250 nm; the uorescence intensity for a given alkane has approximately a Gaussian
dependence on the uorescence photon energy. The uorescence spectrum has been
characterized by the wavelength of maximum k
f
and the full width at the half height r
f
of the emission spectrum. k
f
lies by
f
1 eV below the adsorption onset. This large energy
gap between the absorbed and emitted energy in alkanes (D) is presumably a consequence
of the large dierence between the nuclear distances in the ground and excited states.
Thus, D has a similar meaning as the Stokes shift [25]. For aromatics, where a conjugated
electron system is excited, the Stokes shift is only 0.1 eV. For most compounds studied,
the uorescence quantum yields decline monotonically with the energy of photons used for
excitation. U
f
attens out or reaches a minimum a few tenths of an electron volt above the
liquid phase ionization threshold. The minimum is sometimes followed by a slow increase
[26,27]. The minimum and the slow increase are attributed to the contribution of
recombination uorescence as will be discussed later in this section. Fluorescence was
not detected (U
f
V 10
5
) in the irradiation of geminally substituted branched alkanes, such
as isooctane, and the C
5
, C
7
C
10
cycloalkanes.
The energy of the relaxed S
1
state of alkanes in the liquid phase is certainly
somewhere between the energy of the absorption onset and the energy of the uorescence
maximum. In energy-transfer experiments, the energy of absorption threshold is usually
Table 1 Photon Absorption and Fluorescence Properties of Some Selected Alkanes
Alkanes k
a
, nm
a
k
f
, nm
b
D, eV
c
r
f
, eV
d
U
f,165 nm
e
I
g
, eV
f
I
l
, eV
g
n-Hexane 171 206 1.24 1.02 0.0006 10.18 8.7
n-Decane 173 207 1.19 0.95 0.0042 9.65 8.4
3-Methylpentane 173 231 1.8 1.24 0.0002 10.08 8.5
3-Methylhexane 174 225 1.6 1.14 0.002 10.0 8.65
2,3-Dimethylbutane 175 242 1.95 1.08 0.0061 10.02 8.6
2,3,4-Trimethylpentane 179 244 1.10 0.0016 9.6 8.4
Cyclohexane 177 201 0.83 0.95 0.0088 9.86 8.4
Methylcyclohexane 179 213 1.08 1.1 0.011 9.64 8.3
trans-Decalin 186 217 0.94 1.1 0.023 9.24 8.0
a
Wavelength at which the decadic extinction coecient of the neat liquids equals 5 mol
1
dm
3
cm
1
.
b
Wavelength of uorescence maximum.
c
The dierence between the energies of the absorption onset and the uorescence maximum.
d
Full width at the half height of the uorescence spectrum expressed in energy units.
e
Quantum yield of uorescence measured at 165-nm excitation wavelength.
f
Energy of the gas phase ionization potential.
g
Energy of the liquid phase ionization potential.
Source: Refs. 2527, and 38.
regarded as the energy of the uorescing excited state (S
1
). On the contrary, Kimura and
Hormes, when they constructed term schemes for excited cyclohexane and n-hexane
molecules, used the energy of k
f
as the energy of the lowest lying singlet excited state
[28]. Because of the very low yield of uorescence, other processes, as will be discussed
later, chemical decomposition dominates the decay of alkane excited molecules.
As it is obvious from this review, during the last three decades much information has
accumulated on the properties of singlet excited alkane molecules. At the same time, little
has been known about the properties of triplet excited molecules because there are no
direct methods for studying them [2931]. Our knowledge originates mainly from indirect
sources. Because the S
0
!T
n
optical transitions are spin forbidden, in contrast to S
0
!S
n
transitions, the optical absorption spectra give little information on the triplet energies.
The S
0
!T
n
transitions do appear in the electron-energy-loss spectra, but the resolution of
most of these spectra is poor. The energy of the lowest triplet state of the liquid alkanes
can also be estimated from biphotonic sensitization experiments performed with aromatic
hydrocarbons in alkanes usually in the solid state [3234]. In this process, by consecutive
absorption of two photons, high-energy triplet states of the aromatic molecules are
produced, which by energy transfer may produce the triplet state of the alkane molecule.
The transfer is recognized by the uorescence and phosphorescence properties of the
aromatic molecule [33] or by the decomposition of the alkane molecule [32,34]. The T
1
energies estimated from these experiments, e.g., for the cyclohexanes, are all around 5.8
6.0 eV [29,33,34]. Using another technique, i.e., bombardment of thin lms of alkanes by
low-energy electrons, Leclerc et al. [35] estimated a value of 5.8 eV for the T
1
of n-hexane.
Therefore, the energy separation between S
1
and T
1
is
f
1 eV. For Rydberg-type
excitations, the separation is, as a rule,
f
0.1 eV; for valence-type excitations, it is 12 eV
[22]. The separation of
f
1 eV is in favor of valence excitations in agreement with the
results of those quenching experiments in which the kinetic distance was found to be
comparable with the molecule diameter (Sec. 3.1).
Based on energy-transfer experiments in some works, low-energy (and possibly long-
living) alkane triplet state is also indicated; however, there is no direct proof for its
existence [7,36,37].
According to precise photoconductivity measurements, the ionization onset, which is
usually taken as the ionization potential, is ca. 1.5 eV lower in liquid alkanes than in the
gas phase [38]. The ionization potentials in liquid and gas phases (I
l
and I
g
, respectively)
are related by the equation:
I
1
I
g
P
V
o
1
where V
o
is the lowest energy of the electron-conducting band and P
+
denotes the
polarization energy of the positive ion. P
+
can be represented by Borns equation:
P
c
e
2
2R
o
1
1
e

2
where e is the elementary charge, R
o
is the ion radius, and e denotes the dielectric constant
of the liquid. For liquid alkanes, P
+
has a value between 1.6 and 1.3 eV and V
o
is
between 0.6 and +0.2 eV, so that Eq. (1) predicts a dierence between I
1
and I
g
of
f
1.5
eV in agreement with the experimental values (Table 1).
Passing through the threshold energy for ionization of liquid alkanes, the quantum
yield of ionization, U
i
, increases very slowly with the photon energy [23,26,3840].
According to conductivity and uorescence measurements 1.5 eV above the threshold, U
i
c 0.10.4. Ausloos et al. used chemical decomposition measurements to estimate the
ionization quantum yield of liquid cyclopentane: they reported U
i
= 0.26 F0.05 and 0.4 F
0.1 at energies of 1.3 and 2.9 eV, respectively, above the liquid phase ionization onset [40].
Thus, 13 eV above the ionization threshold the photon absorption mostly produces
neutral excited molecules, so-called superexcited molecules. The photoionization is nearly
complete at 16- to 20-eV photon energies. Ostan and Lipsky suggested that the initially
produced e
+ RH
+
geminate ion pair rst rapidly converts internally to an ion-pair state
ca. 1.6 eV below the liquid phase ionization threshold, then collapses to generate the
uorescent state of RHwith an energy close to its absorption threshold value [26]. Therefore,
in (singlet) recombination uorescing excited molecules form with a high probability.
2.2. Excitation Sources
As mentioned earlier, the light absorption of alkanes causing electron excitation is in the
far-UV range, where the emission of the so-called continuous light sources is little, e.g.,
that of high-pressure mercury or xenon lamps. For photodecomposition measurement,
mostly line-emitting sources are applied. They give a light intensity of 10
15
to 10
16
photon
sec
1
. The photon energies of a nitrogen lamp emitting at 174 nm (7.1 eV) [41], a bromine
lamp emitting at 163 nm (7.6 eV) [42], and a xenon lamp emitting at 147 nm (8.4 eV)
[43,44] are just slightly above the VUV absorption onset of alkanes, but they are lower by
23 eV than the gas phase ionization potential and by 01.5 eV than the liquid phase
ionization onset. The energies of the krypton and argon lamps emitting at 124 nm and at
105107 nm (10 eV and 11.611.8 eV) are the ranges of gas phase ionization potentials
[43]. In liquids, the absorption takes place in an extremely thin layer (
f
1 Am); thus, to
avoid high local conversion and rise of temperature, vigorous stirring is necessary. Some
types of lasers were also utilized for exciting alkanes, e.g., following ArF* excimer laser
excitation with 193 nm (6.34 eV) the nal products were analyzed [45]. Other lasers (e.g.,
N
2
laser, Nd
+
YAG laser, and some dye lasers) in double or multiphoton absorption
mode because of the weak intensities were used only for uorescence measurements or
transient absorption measurements [4650]. In uorescence lifetime measurements apply-
ing the single-photon counting technique, the VUV component of the radiation induced
by electric discharges in medium-pressure (110 bar) gases (H
2
, N
2
, Xe, or air) was also
used [51,52]. In photon absorption and emission studies, synchrotron radiation is often
applied [5356].
Finally, ionizing radiations should be mentioned. A disadvantage of applying
ionizing radiation is that the excited molecule formation is a delayed process; most excited
molecules form probably in electroncation neutralization [7]. Another disadvantage is
that in the irradiated liquid dierently excited molecules and ions are present, including
fragments, which may cause complications, e.g., in energy-transfer measurements.
2.3. Lifetime of the Excited Molecules
For the determination of the excited-state lifetime, s, energy-transfer measurements in
steady-state experiments, orescence decay measurements, or transient photon absorption
measurements were applied.
In steady-state quenching experiments [57,58], usually the ratio of quantum yields of
products or uorescence photons, respectively, measured in the absence (U
0
) and presence
(U) of the quencher showed a linear dependence on the quencher concentration c. From
the linear dependencies, U
0
/U = 1 + Kc, the K quenching parameters were calculated:
K = k
d
s. When energy-transfer experiments were used to deduce the s values, the quench-
ing was assumed to proceed with a diusion-controlled rate, and the transfer was sup-
posed to take place when the acceptor and donor molecules were in contact (no static
quenching). The k
d
transfer rate coecients were calculated using the usual diusional
equations [24,25,59] (see Sec. 3.1).
In Table 2, we show the room temperature ss for some selected alkanes, and among
them there are lifetime data that were determined in quenching experiments. (Data for
larger groups of alkanes are discussed in Refs. 48, 49, 51, 5961, 72, and 73.) For the
Table 2 S
1
Lifetimes (nsec) of Selected Liquid Alkanes at Room Temperature Determined in
Steady-State Excited State Quenching or in Transient Fluorescence and Absorption Studies
Alkanes Quenching Fluorescence Absorption
n-Hexane 0.3 [77];
f
0.32 [48];
V0.7 [59]; 0.7 [73]
0.25 [47];
0.28 [49]
n-Heptane 0.73 [48,60]; 0.9 [51];
1.05 [59]; 1.2 [73]
0.65 [49]
n-Octane 1.08 [48]; 1.35 [81];
1.47 [51]; 1.5 [59]; 1.6 [73]
>1.0 [49]
n-Decane 1.76 [48]; 2.4 [73,81];
2.5 [51,59]; 2.6 [60]; 3.0 [54]
>0.6 [49]
n-Dodecane 2.5 [48]; 3.1 [60]; 3.7 [81];
3.9 [51,59]; 4.0 [73]; 4.2 [54]
>2.8 [49]
n-Tetradecane 3.01 [48]; 4.3 [50,59];
4.4 [73]
n-Hexadecane 3.7 [48]; 5.2 [59] >3.0 [49]
2-Methylbutane 0.75 [59]
2,3-Dimethylbutane 1.0 [81]; 1.4 [59]
Cyclohexane(CH) 1.2 [59] 0.3 [60]; 0.68 [51]; 0.9 [46];
1.1 [59,69,78]; 1.2[72]
>0.3 [49];
1.0 [47]
MethylCH 0.65 [51]; 0.69 [79] 0.81 [48];
1.2 [72]; 1.25 [59]
EthylCH 1.25 [59]
cis-1.2-DimethylCH 1.02 [79]; 1.15 [59]
trans-1,2-Dime.CH 0.9 [59]; 1.11 [79]
cis-Decalin 2.1 [61,63]; 2.18 [51];
2.45 [54]
trans-Decalin 2.24 [48]; 2.7 [59]; 2.82 [51];
2.86 [79]; 3.0 [54]
>1.4 [49];
3.0 [47]
Bicyclohexyl 1.58 [51]; 1.6 [60]; 1.62 [48];
1.8 [54]; 1.9 [72]
n-Dodecane-d
26
6.5 [83]
Cyclohexane-d
12
2.1 [83]; 2.5 [78] 2.7 [47]
Cyclopentane V0.1 [59] 0.1 [49]
Cycloheptane 0.1 [59]
Cyclooctane 0.3 [59]
2,2,4-Trimethylpentane V0.2 [59] <0.01 [47];
0.04 [49]
uorescence lifetime of cyclohexane, the quenching experiments gave 1.2 nsec, a value that
agrees with the results of the newer uorescence and absorbance decay measurements.
The lifetimes of the alkane excited states were generally measured by detecting the
decay of uorescence. The s values obtained by dierent excitations, by x-ray pulses [60,62],
high-energy electron pulses [61,6374], pulses of photons [51,52,54,55,7577], laser pulses
causing double or multiphoton excitations [46,48,50,7883], are generally in good agree-
ment indicating that uorescence originates in each case from the same excited state. These
uorescence lifetimes also agree with the lifetimes that were measured by detecting the
absorbance decay of excited molecules. As regards s, cyclohexane is a special case. For its
excited-state lifetime, Henry and Helman in 1972 suggested 0.3 nsec, based on the very rst
direct measurements [60]. Two years later, Ware and Lyke found 0.68 nsec [51]. However,
over 10 later measurements yielded lifetimes in the 0.8- to 1.2-nsec range: the most probable
room-temperature value is 1.0 nsec.
As shown by Tagawa et al. [74], the alkane excited molecules have a broad absorption
band in the visible region with maxima increasing from
f
430 to
f
680 nm between C
5
and
C
20
for the n-alkanes. This spectrum strongly overlaps with the absorption spectrum of the
radical cations: with lowcarbon atomnumber alkanes the two maxima practically coincide.
With increasing carbon atom number, the red shift in the radical cation absorbance is
stronger than in the S
1
molecule absorbance [47,49,8486]. The decay of the excited
molecule absorbance was composed of two components with 0.1- and 1.0-nsec decay times
in cyclohexane, and 0.17 and 2.7 nsec in perdeuterocyclohexane [47]. The nature of the
faster-decaying component is as yet unclear.
As mentioned before, the excited-state lifetimes determined by photon and (low-
LET) ionizing radiation excitations practically coincide. However, when 5- to 14-keV soft
synchrotron x-rays were used for the irradiation in the experiments of Holroyd et al. [87],
instead of the usual fast electrons with energies in the MeV range, shorter ss were
measured than in VUV photon irradiation. The lifetimes and singlet yields decreased with
decreasing x-ray energy, thus decreased with increasing LET value. This decrease between
14 and 5 keV for cis- and trans-decalin and n-dodecane is ca. 15%. The decrease was
attributed to the quenching of alkane excited molecules by alkyl radicals whose concen-
trations may be as high as 10 mmol dm
3
in the high ionizing density tracks. Shibata et al.
[88] explained similarly the decrease of n-dodecane uorescence lifetime with increasing
LET in heavy-ion radiolysis.
In contrast to the liquid phase lifetimes, those in the gas phase showed marked depen-
dence on the energy of excitation [52,55,75]. They decreased with increasing excitation en-
ergy, and for some alkanes the ss at the red edge in the vapor phase were longer than the
liquid phase lifetimes. For instance, in the 170-nmphotoirradiation of cyclohexane at 1 Torr
pressure, Ware and OConnor found s = 1.21.3 nsec [52], whereas Wickramaaratchi et al.
measured 1.5 F0.2 nsec [75]. The liquid phase value is around 1 nsec. In the literature, there
is no satisfactory explanation for this phase eect. In the lower pressure range, the increase
of the vapor pressure, or added inert gases increased the lifetime because of vibrational
cooling of excited alkane molecules. Most of the energy dependence in the gas phase is
probably because of a competition between relaxation and the chemical decomposition.
In photoirradiated solid cyclohexane (freezing point 6.5jC), much higher uores-
cence quantum yields and longer uorescence lifetimes were observed than in the liquid
phase [89]. In solid Ar matrices, the uorescence characteristics, energy dependence of the
lifetime and intensity, were found to be very similar to these characteristics in the gas
phase. This points to the importance of cyclohexanecyclohexane interactions to deter-
mine the excited-state characteristics in the liquid phase [76].
The lifetime of the triplet excited molecule with energy
f
1 eV below the S
1
energy is
probably extremely short: the triplet excitations are suggested to take place to dissociative
states [90]. Such conclusion can be obtained from the biphotonic sensitization experiments
mentioned in connection with the energy of the triplet states (Sec. 2.1): if the decom-
position had not been fast enough (s V 10
12
sec) due to the back transfer of energy, the
sensitization could not have been observed [29].
2.4. The Radiative Rate Coefficient at
f
25jC
By using the techniques mentioned before, room-temperature ss for about 50 alkanes were
determined. In Fig. 2, we show the uorescence quantum yields as a function of lifetimes.
The U
f
values were generally taken from the work of Rothman et al. [25]; most of the
uorescence quantum yields were measured using 165-nm photons for excitation. This
wavelength is close to the absorption onset of most alkanes and (with the exception of the
smaller molecules) the measured quantumyield is close to the uorescence quantumyield of
the relaxed S
1
molecules [26]. The plot in Fig. 2 is similar to the plot we published in Ref. 59
using only our measurements. Here we use practically all the data that are available in the
literature. For most of the alkanes, several lifetime measurements were published. When
Figure 2 Relationship between lifetime (s) and uorescence intensity (U
f
) for a large group of
alkanes.
these measurements do not dier considerably we use the average. When there are larger
dierences between the results of dierent laboratories we try to select the most probable
value. In Fig. 2, the points representing compounds with similar chemical structure lie
around the same straight line. The slope of the lines in the gure is the ratio of the
uorescence intensity and lifetime (or in other words the product of the uorescence
intensity and the decay rate coecient). Therefore, the slope gives the so-called radiative
rate coecient, R, which is one of the most important photophysical characteristics of
excited states. R is a rate coecient with which the excited molecules would disappear from
the solution if there was no chemical decomposition and only uorescence existed. Five
groups can be distinguished; as the sixth group, we mention the nonuorescing alkanes
whose excited-state lifetimes are extremely short (Table 2):
n-Alkanes, R c 1.6 10
6
sec
1
Methylalkanes, R c 2 10
5
sec
1
Vicinally branched dimethylalkanes, R c 5.3 10
6
sec
1
Cyclohexane and alkylcyclohexanes including deuterated cyclohexane and decalins,
R c 8 10
6
sec
1
Di- and trimethylcyclohexanes, R c 1.2 10
7
sec
1
Nonuorescing alkanes, R < 3 10
3
sec
1
The similarity of R within a class of alkanes (the fact that within a class the points
are on the same straight line) indicates that the properties of excited states are similar. This
is also supported by Lipskys measurements on the uorescence spectra. Within a class the
value of the Stokes shift (D) and the half width of the uorescence peak (r
f
) are nearly
constant (see also Table 1).
For n-alkanes the lifetime increases with the number of carbon atoms in the molecule
together with the increase of the uorescence intensity, whereas the radiative rate
coecient remains constant with a value of
f
1.6 10
6
sec
1
; that is, in the absence of
other competing reactions the excited molecules would decay with uorescence exhibiting
a lifetime of about 600 nsec. Addition of a branch to the carbon skeleton greatly inuences
the photophysical and photochemical properties. In comparison with n-alkanes, r
f
is
larger, the absorption onset is slightly red-shifted, and the emission maximum is strongly
red-shifted (Table 1). These properties point to large nuclear distortions between ground
state and the rst excited state (large Stokes shift, D). The large nuclear distortions lead to
rapid decay, low U
f
, and low R. The high D values of the vicinally substituted 2,3-
dimethylalkanes and other optical properties indicate larger nuclear distortions than those
of the singly substituted ones. These compounds exhibit large uorescence quantum yields
and moderate lifetimes. Their radiative rate coecients are the highest among the aliphatic
alkanes: R c 5.3 10
6
sec
1
.
The S
1
excited-state lifetimes of cyclohexane and alkyl cyclohexanes are relatively
short, all around 12 nsec; however, their U
f
values are relatively high with the result of
relatively high radiative rate coecient:
f
8 10
6
sec
1
. R is the largest for the di- and
trimethylcyclohexane group,
f
1.2 10
7
sec
1
.
In the group of nonuorescing alkanes the lifetimes are very short, s V 0.3 nsec; an
upper limit of R < 3 10
3
sec
1
is estimated. The absence of uorescence for these
compounds may have two causes: the low R, i.e., low rate coecient of the S
1
!S
0
radiative transition and the short lifetime, i.e., the very fast chemical decomposition. In the
C
5
and C
7
C
10
cycloalkanes the ring strain, which is mainly caused by the repulsive
interaction of their unfavorably displaced H atoms, may enhance the rate coecient of the
chemical decay by CH decompositions. In the excited sates of the geminally branched
alkanes the excess energy strongly localized to the branch points can cause rapid local
decomposition.
2.5. Temperature Dependence of the S
1
Lifetimes, Depopulation
of S
1
Excited Molecules
In the early eighties, several papers [7981] reported that the uorescence lifetime exhibits
characteristic temperature dependence: it increases with the decreasing temperature and
tends to level o at low temperature. The Arrhenius plots, log s
1
versus T
1
, did not give
straight lines. In photophysics, such behavior is usually interpreted in terms of several
competing decay channels, and the description is usually made by the sum of several
Arrhenius-type decays. Because at higher temperatures the k decay rate coecient (= s
1
)
can be well described by a single Arrhenius-type equation, the following description was
introduced by Orlandi et al.:
s
1
k k
0
A expE
a
=RT 3
According to this equation the decay is composed of a temperature-independent and a
thermally activated part [55,67,7577,7983]. For cis- and trans-decalins, however, the
temperature dependence was found to be very small [62,67,79,80]. Because of the small
temperature dependence, the activated and nonactivated processes were not separated.
The k
0
, A, and E
a
parameters obtained for a few alkanes are collected in Table 3. k
0
is around 10
8
sec
1
, A c10
11
to 10
12
sec
1
, and E
a
c10 to 20 kJ mol
1
. In principle, the
decay of excited states may involve S
1
!S
x
-type internal conversion transitions [IC, where
S
x
is some singlet state that gives the product(s) of chemical decomposition] and S
1
!T
n
-
type intersystem crossing processes (ISC). The temperature-independent decay was
attributed, on the basis of the size of the rate parameter (k
0
c 10
8
sec
1
), to S
1
!T
n
-
type intersystem crossing. At the same time the temperature-activated decay with a fre-
quency factor of A c 10
11
to 10
12
sec
1
was attributed to an internal conversion process
that takes place by overcoming a barrier of E
a
c1020 kJ mol
1
and leads nally to some
Table 3 Temperature-Independent Term (k
0
), Preexponential Factor (A), and Activation Energy
(E
a
) Obtained by Using Eq. (3) for Selected Groups of Alkanes
Alkanes
k
0
, sec
1
A, sec
1
E
a
, kJ
mol
1
U
nonact.
U
act.
U
radical
U
molec.
n-Octane 2.9 10
8
1.1 10
11
14 0.4 0.6 0.2 0.8
n-Decane 1.5 10
8
5.3 10
11
18 0.3 0.7 0.2 0.8
2,3-Dimethylbutane 5.2 10
8
2.0 10
11
15 0.5 0.5 0.5 0.5
Cyclohexane (CH) 3.6 10
8
1.6 10
11
13 0.3 0.7 0.2 0.8
MethylCH 3.4 10
8
7.5 10
11
16 0.2 0.8 0.3 0.7
trans-1,4-DimethylCH 2.9 10
8
6.8 10
11
18 0.4 0.6 0.4 0.6
cis-1,3-DimethylCH 3.6 10
8
2.1 10
12
20 0.4 0.6 0.5 0.5
IsopropylCH 7.1 10
8
7.5 10
12
18 0.6 0.4 0.6 0.4
The table also shows the quantum yields of nonactivated and activated processes and the yields of the radical-
forming and unimolecular reactions.
Source: Refs. 29, 67, 79, and 81.
singlet state of the products. We summarized the reaction possibilities and their identi-
cation in Fig. 3. (The chemical reactions shown in the gure will be discussed later.)
The identication of the temperature-dependent decay with S
1
!S
x
IC and the tem-
perature-independent decay with S
1
!T
n
ISC was conrmed by investigations on xenon
heavy-atom eect and on deuterium eect as well. Heavy atoms are known to increase the
rates of spin-forbidden processes, whereas the rates of spin-allowed processes remain
essentially unchanged. In agreement with the expectations, the A preexponential factor
and the E
a
activation energy were found to be unaected by the presence of Xe added to the
samples at a concentration of 0.10.4 mol dm
3
[67,82]. At the same time k
0
was found to
increase. For deuteration, the eect was just the reverse. The IC process is connected with
chemical decomposition; for the investigated compounds the chemical decomposition was
mainly H
2
elimination, and therefore its rate should be inuenced by deuteration. At the
same time, the ISC process is connected with multiplicity changes only; therefore the eect
of deuteration on that process should be negligible, in agreement with the experimental
ndings [83].
2.6. Characteristic Decomposition Modes of the Low-Energy Excited
Alkane Molecules
The photodecomposition of n-alkanes at excitation energies slightly above the absorption
onset involves both CH and CC bond decompositions [18]. The dominant process is the
CH scission, U(H
2
) = 0.80.9, and the contribution of CC decomposition is small. In
the photolysis of cyclohexane, cycloheptane, cyclooctane, and cyclodecane, however, only
hydrogen evolution was observed [U(H
2
) c 1]. In the photolysis of cyclopentane, CC
decomposition also takes place with low yield. In the reactions of cyclopropane and
Figure 3 Schematic representation of formation and decay of alkane S
1
excited molecules.
cyclobutane, the ring decomposition is the decisive process; the yield of CH decom-
position is very low. The branchings on the carbon skeleton in isoalkanes and alkyl
cycloalkanes increase the yield of CC decompositions: the highly branched alkanes such
as 2,2-dimethylbutane or 2,2,4-trimethylpentane decompose mainly by CC bond scissions
at the branch points.
H
2
and H Elimination
The mechanism of H
2
formation involves both unimolecular H
2
elimination, when both of
the H atoms of a hydrogen molecule originate from the same alkane molecule, and H atom
elimination with subsequent H atom abstraction reaction. We show the mechanism on the
example of cyclohexane photolysis (hm = 7.6 eV) [91]:
c C
6
H
12
!
hm
c C
6
H
12
* 4
c C
6
H
12
!c C
6
H
10
H
2
UH
2
u
0:85 5
!c C
6
H
.
11
H UH 0:14 6
!c C
6
H
12
hmV U
f
0:01 7
H c C
6
H
12
!c C
6
H
11
.
H
2
8
2c C
6
H
11
.
!
k
d
c C
6
H
12
c C
6
H
10
9a
!
k
c
c C
6
H
11
2
9b
The H atom detachment in Eq. (6) is followed by H atom abstraction from another
cyclohexane molecule in Eq. (8) and the cyclohexyl radicals disappear in disproportiona-
tion and combination reactions giving in nearly equal amounts cyclohexene and dicyclo-
hexyl end products. In the liquid phase, the secondary decomposition of the primarily
formed energy-rich reaction products is of minor importance because of the eective
collisional deactivation. This is in contrast to the gas phase reaction, where the primarily
formed products readily undergo decomposition in the absence of deactivation (at low
pressures), e.g.:
c C
6
H
12
* !
H
2
c C
6
H
10
!C
2
H
4
C
4
H
6
5a
The yield of unimolecularly formed cyclohexene, and by that the yield of unim-
olecular H
2
elimination (quantum yield in photolysis or G value in radiolysis), X(H
2
), may
be calculated from the yields of alkene and dimer dehydrogenation products by the
relation [91,92]:
XH
2
u
Xalkene k
d
=k
c
Xdimer 10
where k
d
/k
c
stands for the disproportionation-to-combination ratio of the relevant radicals.
Using a value of 1.1 for this ratio and the yields of cyclohexene and bicyclohexyl U(H
2
)
u
=
0.85 and G(H
2
)
u
=1.31.5 has been calculated. The molecular and atomic channels can also
be distinguished by applying the isotope dilution technique, introduced by Dyne [93] and
Dyne and Denhartog [94].
The quantum yields and G values of H
2
elimination for a larger group of alkanes are
collected in Table 4; the values were mostly determined by using Eq. (10). Because in the
photolysis and radiolysis of the n-alkanes shown in the table various kinds of radicals are
produced simultaneously (e.g., n-propyl and sec-propyl from propane), the weighted
averages of several k
d
/k
c
values were used in Eq. (10). The ratios can be determined by
suppressing the radiolytic alkene and dimer yields in the presence of radical scavenger
(e.g., I
2
):
k
d
k
c
DGalkene
DGdimer
11
As shown in the table, during photolysis of n-alkanes and C
5
C
10
cycloalkanes,
U(H
2
)
u
is 0.70.9, slightly exceeding the values of 0.60.7 measured at low photon energies
in the gas phase [18,19]. Cyclopropane and cyclobutane undergo H
2
elimination to a
negligible extent: U(H
2
)
u
c0.02. The value of U(H
2
)
u
in branched alkanes is much smaller
than in normal and cyclic alkanes. The results obtained in the gas phase show that the
yields decrease with the increasing branching [18]: for instance, in the series of C
5
H
12
isomers, the isomer with maximum branching, neopentane, essentially does not eliminate
hydrogen [16].
In connection with the gas-phase studies, it was rst suggested at the beginning of the
1960s [95,96] that the H
2
elimination from the lower-molecular-mass alkanes takes place
mainly from a single carbon atom (1,1 elimination) and not from two neighboring ones
Table 4 Quantum Yields and G Values of Unimolecular H
2
Elimination and the G Values of S
1
Molecule Yields Estimated from the Yields of Unimolecular Hydrogen Elimination
Alkanes U(H
2
)
u
Energy, eV G(H
2
)
u
G(S
1
)
Propane 0.76 8.4 1.4 1.8
n-Pentane 0.82 8.4 1.4 1.7
n-Hexane 0.9 7.6 1.48 1.6
n-Heptane 0.9 7.6 1.31 1.5
n-Octane 0.92 7.6 1.4 1.5
Cyclopentane 0.88 7.6 1.6 1.8
Cyclohexane (CH) 0.85 7.6 1.3 1.5
Cycloheptane 0.89 7.6 1.3 1.6
Cyclooctane 0.87 7.6 1.9 2.2
Cyclodecane 0.91 7.6 2.0 2.3
2,2,4-Trimethylpentane 0.08 8.4
Methylcyclopentane 0.46 7.6
Methylcyclohexane 0.7 7.6
Ethylcyclohexane 0.63 7.6
cis-1,2-DimethylCH 0.28 7.6
trans-1,2-DimethylCH 0.21 7.6
cis-1,3-DimethylCH 0.5 7.6 11.5 23
trans-1,3-DimethylCH 0.53 7.6 0.51 12
cis-1,4-DimethylCH 0.45 7.6
trans-1,4-DimethylCH 0.45 7.6
(1,2 elimination). In liquid-phase radiolysis experiments, 1,1 elimination was also dem-
onstrated by deuterium-labeling experiments [97,98]:
-CH
2
-CH
2
-*!
H
:::::::
H
j j
CH
::::
CH !
H
2
1;2 elimination
CHjCH 12
-CH
2
-CH
2
-* !
H
2

C CH
2
!
1;1 elimination
CHjCH 13
As a result of 1,1 elimination, a carbene intermediate remains that quickly rearranges to
alkene. During the photolysis and radiolysis of cycloalkanes with 710 carbon atoms,
apart from the formation of the usual cycloalkene products, dehydrogenation into
cycloalkanes with interesting bridged rings was also observed [99102]. Similar products
were also found in catalytic reactions [103]. The cross-bridged products are formed by
stabilization of the carbene in transannular insertion. During photolysis of C
7
C
10
cycloalkanes, the distribution of products remaining after H
2
elimination in several
solvents [99] agreed with the distribution of products formed during stabilization of
carbenes produced in an independent way, by the UV photolysis of cycloalkanone p-
tosylhydrazones under aprotic conditions, e.g., for the C
8
ring:
Photolysis of
diazo compound (%)
54 43 3
Radiolysis (%) c60 c37 3
7.6-eV
photolysis (%)
57 41 2
It means that the H
2
elimination from these compounds takes place exclusively through
1,1 elimination [99,100].
Alkane and Alkyl Radical Elimination
In the alkane elimination, a smaller alkane and an alkene molecule are formed in the decay
of excited molecule without intermediate radicals. A few examples of this reaction are
shown in Table 5. Homolytic split of alkane molecules to two alkyl radicals and the
subsequent reactions of radicals may give the same products. Radical-scavenging techni-
ques or deuterium-labeling studies may be used to distinguish the two processes. Although
liquid phase elimination has rarely been investigated, a great amount of data are available
in the literature concerning the reaction in the gas phase. For example, Ausloos et al. [16]
using partially deuterated compounds, showed that in the photolysis of isopentane during
methane elimination (from position 1) the H atom is taken o with comparable
probability from positions 2 and 3:
5 CH
3
j
CH
3
---
1
CH
2
- CH
2
3
- CH
3
4
Alkane elimination has a low yield during the photolysis of liquid n-alkanes (e.g., n-
pentane [104,106]). This reaction takes place with high yield only for branched alkanes
where it is likely to be a main primary-decomposition step [105,107].
Isomerization of Cycloalkanes into Aliphatic Alkenes
Alkylcyclopentanes and cyclohexanes rearrange to aliphatic alkenes during both photol-
ysis and radiolysis [108113]. The double bond in the product aliphatic alkenes can be
found connected to one of the carbon atoms taking part in ring opening. The derivation of
Table 5 Quantum Yield of Alkane Elimination in the Photolysis
of Some Liquid Alkanes
Propane, 8.4 eV [105] U
C
3
H
8
* ! C
2
H
4
+ CH
4
0.1
n-Pentane, 8.4 eV [104]
C
5
H
12
* ! C
2
H
4
+ C
3
H
8
0.06
! C
3
H
6
+ C
2
H
6
0.05
! C
4
H
8
+ CH
4
0.1
Isobutane, 8.4 eV [105]
C
4
H
10
* ! C
4
H
8
+ CH
4
f
0.5
2,2-Dimethylpropane, 7.6 eV [107]
C
5
H
12
* ! iso-C
4
H
8
+ CH
4
0.57 F 0.14
2,2,4-Trimethylpentane, 7.6 eV, 8.4 eV [104,106]
C
8
H
18
* ! iso-C
4
H
8
+ iso-C
4
H
10
0.36
! C
3
H
6
+ neo-C
5
H
12
0.05
! C
7
H
14
+ CH
4
0.17
the alkenes formed is shown schematically on the example of ethylcylohexane:
From this compound as well as from other alkylcyclohexanes the yield of ring-opening
products is relatively small, about U = 0.10.4, and G = 0.31.6 [108,110] (Table 6), while
usually the main decomposition process is the hydrogen formation, which leaves the cyclic
structure intact. Here, and with the other alkylcyclohexanes and alkylcyclopentanes, the
scission of the ring to smaller molecular mass alkenes and cyclopropane derivates was
detected with very low yield.
It was an important observation fromthe point of viewof the opening mechanismthat
in dimethylcyclohexane isomers the yield of transformation from cis into trans and from
trans into cis also takes place. In the 7.6-eV photolysis of 1,2-dimethylcyclohexanes the cis
formisomerizes to trans with a yield of U(c!t) =0.12, while the reversed reaction has a yield
of 0.07. In the photolysis of 1,3-dimethylcyclohexanes U(c!t) = 0.07 and U(t!c) = 0.15,
Table 6 Quantum Yields and G Values of C
n
H
2n
Aliphatic Alkenes in the 7.6-eV Photolysis
and Radiolysis of C
n
H
2n
Cycloalkanes
C
n
H
2n
cycloalkane U (aliphatic alkenes) G (aliphatic alkenes)
Cyclopentane 0.04 0.88
Cyclohexane No product 0.34
Methylcyclohexane 0.10 0.62
cis-1,2-Dimethylcyclohexane 0.37 1.50
trans-1,2-Dimethylcyclohexane 0.39 1.60
trans-1,3-Dimethylcylohexane 0.10 0.60
trans-1,4-Dimethylcyclohexane 0.17 0.73
In radiolysis a fraction of C
n
H
2n
alkenes forms in bimolecular radical reactions.
Source: Refs. 18, 29, 108, 110, and 111.
while for the 1,4-dimethylcyclohexanes U(c!t) = 0.13 and U(t!c) = 0.06 [108]. Similar
phenomena were observed during the radiolytic processes as well [110,112]. In dimethylcy-
clohexanes the methyl groups as substituents can be of equatorial position, falling into the
plane of the ring, or of axial position, roughly perpendicular to this. If the chair form of
cyclohexane rearranges intoanother chair form, the axial and equatorial substituents change
their positions, i.e., the axial position turns into the equatorial one and vice versa in the
dimethyl-cyclohexanes. Both (e,e)X (e,a) and (a,a)X (e,a) transformations can take place
through the previous dissociation of at least one bond of the molecule.
In all cases when photolytic isomerization into aliphatic alkanes was observed it was
found that the quantum yield of primary decomposition calculated from the measured end
products is slightly smaller than unity.
On the basis of these results it is assumed that isomerization to aliphatic alkenes
proceeds through alkyl biradicals whichapart from alkene formationcan reclose again
into the initial cycloalkanes giving in this way products not measured by the usual
techniques. In 1,2-, 1,3-, and 1,4-dimethylcycloalkanes, reclosing can also result in the
opposite isomer, thereby providing a possibility for the observation of the process. The
biradical may also fragment yielding ethylene and a smaller biradical. The cyclopropanes
observed among the products may form in stabilization of the 1,3-biradicals.
Correlation Between Photophysical and Photochemical Data
Because uorescence plays a very small role in the depopulation of alkane excited
molecules the sum of the quantum yields of the chemical decompositions in the thermally
activated and nonactivated channels is practically unity: U(S
l
!S
x
) + U(S
l
!T
n
) is 1.
Using Eq. (3), the temperature dependencies of the product yields formed in the activated
and nonactivated channels have the following forms:
US
1
! S
x

A expE
a
=RT
k
0
A expE
a
=RT
15
US
1
! T
n
1 US
1
! S
x
16
According to these equations, the product formation in the S
1
!S
x
activated channel is
increasing with the increasing temperature, whereas the product formation in the S
1
!T
n
nonactivated channel is decreasing. Xenon is expected to have an opposite eect on the
yields. The temperature and Xe eect studies showed that the H
2
elimination is related to
the activated channel, and the H atom elimination to the nonactivated [67,79,81,113]. In
the 7.6-eV photolysis of n-decane between 20 and 45jC, U(H
2
)
u
increased from 0.62 to
0.82, whereas U(H) decreased from 0.4 to 0.08. Xe in a concentration of 0.2 mol dm
3
decreased U(H
2
)
u
and increased U(H) by
f
20% [67]. In cycloalkane photolysis, the yields
of ring-opening products showed a denite nonactivated character: in the temperature
range mentioned, the yield of linear octenes from ethylcyclohexane decreased from 0.32 to
0.13; Xe increased the yield by
f
25% [113]. From the point of view of activated and
nonactivated character the CC decompositions in aliphatic alkane photolysis were not
investigated. However, based on the values of the yields, the alkane elimination was
tentatively identied as a singlet decomposition, and the homolytic split to two alkyl
radicals as a triplet decomposition [81]. In Table 3 we show for some selected alkanes the
quantum yields of the decompositions in the activated and nonactivated channels at 25jC
calculated using Eqs. (15) and (16). The table also contains the yields of unimolecular
(hydrogen and alkane) eliminations and the yields of radical-forming (H atom elimination,
CC scission to radicals or biradicals) reactions. The correlation between the yields of
activated decay channel and the unimolecular decompositions and between the yield of the
nonactivated decay and the yield of radical/biradical forming reactions supports the
identications of the individual decomposition types.
The very small temperature dependence in the decay of excited cis- and trans-decalin
molecules may be interpreted in terms of absence of thermally activated decay. The
chemical decomposition of excited decalin molecules yields a large number of products
making the identication of the individual decomposition channels and the determination
of their yields rather complicated [81,114]. However, from the distribution of products it is
certain that the yield of H
2
elimination is low, and the majority of H
2
formation, U(H
2
) =
0.42 and 0.50 for cis- and trans-decalin, respectively, originates via H atom formation and
H abstraction. Another important reaction is the CC bond decomposition yielding
probably a biradical. The formation of C
4
cyclo-C
6
products, cyclodecenes, and partly
also cis!trans/trans!cis isomerizations observed in 7.6-eV photolysis is probably due to
the stabilization of these biradicals. Both the H-atom- and the biradical-forming reactions
occur with a high probability at the tertiary carbon atoms: previously these reactions were
attributed to nonactivated (triplet) decompositions. Therefore, the absence of temperature
dependence in the excited molecule decay is probably because of a strong localization of
the excitation energy between the two tertiary carbons where there is no possibility for
molecular elimination reaction.
2.7. Energy Dependence of the Primary Decomposition
Similarly to the uorescence quantum yields, the yields of individual primary decom-
position steps generally show considerable excitation energy dependence: the yields of the
unimolecular H
2
and alkane eliminations and also those of the radical-type decomposi-
tions show a continuous variation with photon energy [27,39,42,107,115]. In cyclohexane
photolysis the sum of the quantum yields of the two primary decompositions described by
Reactions (5) and (6) is practically unity between photon energies 7.6 and 11.6 eV: U(H
2
)
u
+ U(H) c 1. Close to the absorption threshold the H
2
elimination predominates: at 7.6
eV U(H
2
)
u
= 0.85. The yield decreases with the energy, U(H
2
)
u
= 0.78 and 0.64 at 8.4 and
10.0 eV, and it is only 0.4 at 11.6 eV. Thus, at the highest energy the yields of H
2
and H
elimination are comparable.
In the photolysis of cyclopentane [39,116] the energy dependencies of the H
2
elimination and H atom detachment are very similar to the energy dependencies of these
processes in cyclohexane photolysis. However, in cyclopentane photolysis ring decom-
position is also observed producing 1-pentene and ethylene + C
3
H
6
U(1-pentene) = 0.05,
U(C
2
+ C
3
) = 0.05 at 7.6 eV]. The yields of both ring decomposition reactions were found
to increase with the increasing photon energy at the expense of hydrogen formation.
The product yields in the photolysis of n-pentane, n-hexane, n-octane, and n-decane
also show decreasing importance of H
2
elimination and increasing importance of H atom
detachment with the increasing photon energy [27,117].
In contrast to the results obtained with n-alkanes and cycloalkanes, H
2
elimination is
found to be an unimportant process in the photolysis of neopentane [107]. At 7.6 eV the
methane elimination and direct CC bond cleavage to radicals are the predominant
processes:
neo-C
5
H
12
*!CH
4
iso-C
4
H
8
U 0:57 F 0:14 17
neo-C
5
H
12
*!CH
.
3
t-C
4
H
.
9
U 0:38 F 0:14 18
With an increase in photon energy, the importance of the radical-forming reaction increases
at the expense of the methane elimination process.
The energy dependence of the photodecomposition is attributed to an energy-
dependent relaxation of the higher excited molecules to the relaxed S
1
state. When the
photon energy is higher than the energy of the ionization onset ionic processes may also
contribute to the energy dependence. Although there are not enough measured data to
make a denite conclusion, from the published data it seems that when the energy is
increased above the ionization threshold the yield of the molecular-elimination-type
reactions continues to decrease and that of the radical-type reactions continues to increase.
Thus the chemical decomposition does not parallel the uorescence where sometimes an
increase in the uorescence yield was observed (Sec. 2.1). The energy dependence is higher
for the smaller molecules than for the larger ones.
The ionization, electroncation recombination, and the time scale of formation,
relaxation, and decay of alkane excited molecules were studied several times in pump-and-
probe-type subpicosecond laser experiments [49,118120]. Sander et al. [49] used 0.4-, psec
248.5-nm laser excitation in the double-photon mode. At their probe wavelength of 497
nm, both the excited molecules and the radical cations contribute to the light absorption.
These experiments may supply direct data on the time scale of relaxation. After the fast
rise of absorbance during the laser pulse there is a 0.4- to 1.4-psec ultrafast component of
absorption decay that they attribute to fragmentation from higher singlet excited states,
which competes with internal conversion to the S
1
state of the parent molecules. The fast
component is followed by a 5- to 15-psec slower component in which for some alkanes there
is a re-rise of absorbance. They attribute the second component to geminate recombination.
A third component is due to the S
1
molecule decay. It should be noted, however, that other
pump-and-probe experiments, e.g., the fsec transient measurements of Long et al. [119],
suggest much faster geminate recombination than those proposed by Sander et al. Thereby,
these experiments contradict the view of Sander et al.
It would be elegant to nish the part on photophysics and photochemistry of liquid
alkanes by giving a picture that unies the temperature- and energy-dependence results
obtained in uorescence and photodecomposition studies. However, the spectroscopic
information available for alkane molecules is not sucient to identify the exact excited
states involved in the radiative and nonradiative processes [55]. Because of the lack of
information, there are dierent views on the positions and identities of excited states
involved [52,55,83,121,122].
In Fig. 4 we try to explain and, where it is possible, to unify the dierent views using
the usual simplied two-dimensional potential energy diagram for CH bonds. The
potential energy curve of S
1
along the length of a CH bond is displaced to higher R
CH
nuclear distances (reaction coordinate) to explain the strong nuclear distortions and large
Stokes shift reected by uorescence. This is in contrast to the views of Plotnikov [122]
and Flamigni and Orlandi [83]: they assumed that the potential energy surfaces of the S
0
and S
1
states are essentially identical, except that S
1
is shifted to higher values by
f
7 eV,
because, in their opinion, the excitation energy of S
1
is delocalized over the entire
molecule. Other authors, however, suggest strongly localized alkane excited states. From
the S
1
potential energy curve, by passing through a small E
a
energy barrier S
x
can be
reached, which, according to the suggestion of Orlandis group, may give the carbene +
H
2
decomposition products. Wichramaaratchi et al. suggest a dissociative state denoted by
S
2
(this is shown in the gure), which crosses S
1
, and the crossing point lies near a very low
vibrational level of S
1
, thereby promoting S
1
!S
2
IC. S
2
is assumed to be responsible for
two reaction channels: one leading to molecular H
2
and other leading to atomic H [55]. If
H atom elimination is of lower importance from this state, S
1
!S
2
IC in the mechanism
suggested by Wichramaaratchi et al. is practically identical with S
1
!S
x
used in the
terminology of Orlandis group. The authors of Refs. 55, 83, 121, and 122 all agree that
there is a dissociative triplet state, T
n
, which can easily be populated by ISC from S
1
. We
show the potential energy curve of this state (T
n
) as it has been suggested by Orlandi et al.
[83,121]. This state gives only radical decomposition products. In order to explain the
results of the biphotonic sensitization experiments (Sec. 2.1) another triplet state
f
1 eV
below S
1
(T
1
) is also needed. Most probably, this triplet is also dissociative.
The proposed mechanism may explain such excited-state characteristics as the
temperature dependence of lifetime or k
ex
dependence of the uorescence intensity at
low excitation energies. However, in order to explain the energy dependence of the
photodecomposition at high energies at least one more dissociative state should be
included in the mechanism, which decompose to radicals.
3. ENERGY TRANSFER
Energy transfer from an electronic excited state of an alkane molecule to a solute molecule
was rst suggested 50 years ago [123]. Since then over 100 papers discussed the various
Figure 4 Two-dimensional potential energy curve for CH bond decomposition.
aspects of the transfer, e.g., the properties of excited states involved in the transfer
(reaction diameter, lifetime) or the nature of the transfer reaction (diusional type with
short-range contact interaction, Forster type). An important practical aspect of the subject
is the protecting eect exerted by dierent additives on radiation induced decomposition
of saturated hydrocarbon systems (lubricants, insulators, polyethylene). Most frequently,
the transfer in liquid cyclohexane was studied, but a few papers discussed the transfer
reactions also in decalins, 2,2,4-trimethylpentane, and n-alkanes. Mostly the low solute
concentration region was studied; however, by photoexcitation or radiolysis in some
alkanealkane mixtures the product formation, and by that the energy transfer, was
investigated in the entire concentration range [124126]. The techniques used to obtain
transfer data include stationary photolysis or radiolysis with detection of nal products or
uorescence intensity, pulsed photon or electron irradiation, and detection of transient
uorescence or absorbance.
3.1. Energy Transfer from the S
1
Excited State
Based on the magnitude of the transfer rate coecients and other transfer characteristics it
is obvious that in the energy transfer from alkane excited states to solutes long-range
interactions play a minor role (Forster-type energy transfer) [70,127]. In the Forster-type
energy transfer, the overlap of the donor emission and the acceptor absorption spectra
determines the transfer rate coecients. However, in the quenching of alkane excited states
no correlation was found between the overlap integrals and the transfer rate coecients:
the transfer is suggested to take place because of short-range contact interactions.
Therefore, in the transfer mutual diusion of the reactants to each others proximity
has a determining role. The diusional character is also supported by the temperature
dependence of the transfer rate coecient; this dependence practically agrees with the
temperature dependence of the diusion [42,62,64,128]. However, the simple Stokes
EinsteinSmoluchowski equation (SES), k
d,SES
= 8RT/3000g, where g is the solvent
viscosity at temperature T, fails to describe properly the values of transfer rate coecients
[42,129131]. In alkane excited state quenching, where the lifetimes are short (s c1 nsec),
and the quencher concentrations are high, c = 0.010.2 mol dm
3
, perhaps static
quenching eects and also transient quenching eects play a role in the transfer in
addition to the usual diusional quenching [131].
When the reaction radius is larger than the sum of the molecular radii of the reacting
molecules, there is an instantaneous quenching by the quencher molecules that reside
inside the reaction radius of the excited molecule, rV (also called kinetic distance), in the
moment of excitation. The term that takes into account instantaneous quenching is called
static quenching term and usually has the form of exp(NV
1
c), where c is the quencher
concentration and N is Avogadros number. V
1
is dened as the volume around an excited
molecule, where instantaneous quenching occurs:
V
1

4p
3
rV
3
r
3
19
r (= r + r
s
) is the collision distance, i.e., the sum of the molecular radii of the solute and
solvent molecules.
The quencher molecules that are near the excited molecule in the moment of
excitation have a much higher probability for depleting the excited molecules than the
other quencher molecules. For that reason the rate coecients used to describe the decay
of excited molecules often have a so-called transient term, k
0
r
1
(pDt)
1/2
: the transient term
has some importance only at short times (t), much shorter than the natural lifetime of the
excited molecule.
The third term k
0
is the usual diusion controlled rate coecient: k
0
= 4pNrVD, where
D = D
S
+ D
s
is the sum of the diusion coecients of the solute and solvent molecules.
In the literature there are several, mostly just slightly dierent, equations that describe
the rate coecient of the diusion controlled reactions: these equations are usually based on
the solutions of Fick II diusion law assuming that the reaction probability at contact
distance is 1. Andre et al. [131] used the following equation to describe the time dependence
of excited molecule concentration [RH*] produced by an innite excitation pulse:
RH* RH*
0
expNV
1
cexpk k
0
c1 2rVpDt
1=2
t 20
In Eq. (20), k is the rate coecient of the excited molecule decay without quencher (k =s
1
).
Using this equation in Fig. 5, we show the time dependence of the relative excited
cyclohexane molecule concentration in a solution containing 0.05 mol dm
3
CCl
4
. In order
to show the eect of static quenching we chose a large reaction radius of rV = 1.3 nm. It is
Figure 5 Decay of excited cyclohexane molecules in the pure liquid and in solution containing 0.05
mol dm
3
CCl
4
. Parameters used for the calculations: k =1.05 10
9
sec
1
[67], rV =1.3 nm[64], r =
0.7 nm, and D = 3 10
9
m
2
sec
1
[59].
obvious from Fig. 5 that static quenching is important in stationary experiments; however,
when the rate coecient is calculated from decay measurements, the static quenching,
because of its instantaneous nature, is unobserved. In pulsed experiments, the quenching
rate coecient has the form of Eq. (21):
k
d
k
0
1 rVpDt
1=2
21
For stationary experiments, Andre et al. [131] suggest the form:
k
d
NV
1
s
1
k
0
1 rVDs
1=2
22
In the usual treatments there is only one parameter to be tted, i.e., the reaction
radius. In practice three cases should be distinguished:
1. The kinetic distance exceeds the collision distance, r > r, which is typical for
Forster-type energy transfer, but as mentioned before there is evidence against this
type of transfer in alkane systems. The reaction radius may also be high if the
transfer takes place froma large-orbit Rydberg state. In early studies using steady-
state quenching or uorescence decay experiments, high kinetic distances in the
order of 1.5 nmwere suggested for cyclohexane and the decalins [42,64,129]. Most
of the later studies agree, however, that the largest kinetic distance values
practically agree with the contact distances (
f
0.70.8 nm) or they are just slightly
larger. This result suggests that the relaxed excited states of these alkanes do not
have large orbit character and that static quenching has a minor role in the
transfer.
2. When rV cr (=0.8 F0.2 nm) the reaction probability is 1 at the contact distance.
This condition is fullled for good quenchers such as CCl
4
, SF
6
, uorinated
hydrocarbons, and in some experiments alkenes or benzene [70,128,130,132].
When rV V r, the term NV
1
= 0.
3. When rV < r not all of the encounters lead to quenching. The p reaction
probability may be calculated as the ratio of the measured and calculated rate
coecient using rV = r: p = k
q
/k
d
. Reaction probability values determined for
larger groups of quenchers in cyclohexane or n-hexadecane have been reported
in Refs. 70 and 130.
For the description of partially diusion-controlled energy-transfer reactions often
the reaction scheme and theory introduced by Rehm and Weller [133] as well as by Balzani
et al. [134] are applied:
RH* Q X
k
d
k
d
RH*
: : : : :
Q X
k
e
k
e
RH
: : : : :
Q* X
k
d
k
d
RH
# 1=s
Q*
# 1=s
q
23
where k
d
and k
d
are the rate coecients of the formation (diusion-controlled rate
coecient) and dissociation of the encounter pair, respectively, and k
e
and k
e
represent
the rate coecients of the energy transfer step and its reverse, respectively. For the energy-
transfer step one can write:
k
e
k
e
expDG=RT 24
k
e
k
0
e
expDG
=RT 25
DG is the free energy change of the forward energy transfer and k
e
0
and DG
+
are the
preexponential factor and the free energy of activation of its rate coecient, respectively.
DG can be approximated by the energy dierences of excited states of donor and acceptor
molecules:
DGcDE ERH*S
1
; RHS
0
EQ*S
1
; QS
0
26
DG
+
is given by the RehmWeller theory:
DG

DG
2

DG
2

2
k
4

2
" #
1=2
27
k is often an adjustable parameter that is connected with reorganization of the inner
coordinates of the reactants and reorganization of solvent molecules. For a given donor
molecule and chemically similar acceptor molecules, k is assumed to be constant. When k
is small and in Eq. (28), which is developed to describe the transfer rate coecient
assuming 1/s
q
>>k
d
c, the second term in brackets, (k
d
/k
e
0
) exp(DG
+
/RT), can be
neglected, we get the so-called Sandros equation (29):
k
q
k
d
1 exp
DG
RT

k
d
k
0
e
exp
DG
RT

1
28
k
q

k
d
1 expDG=RT
29
For excited alkane donors k is assumed to be high. Eq. (28) was often used to evaluate the
molecular structure dependence of the transfer coecients [69,70,127,135,136]. In Fig. 6,
we show the rate coecients of the energy transfer from excited cyclohexane molecules to
alkanes, alkenes, and benzene as a function of the DE energy dierence based on the
experiments of Hermann et al. [135]. The solid lines were calculated with k
d
= 2 10
10
mol
1
dm
3
sec
1
and k = 0.5 or 1 eV. Using a similar treatment to describe the energy
transfer from excited cyclohexane molecules, Busi and Casalbore [127] obtained the best t
with k
d
= 3.5 10
10
mol
1
dm
3
sec
1
and k = 0.55 eV. For n-hexadecane solutions a
lower value of k
d
was applied,
f
1 10
10
mol
1
dm
3
sec
1
[70]. The calculations again
strongly support that the transfer occurs with a collision mechanism and the free energy
dierence determines the rate coecient of the energy-transfer step.
Seemingly, a dierent mechanism determines the rate of energy transfer to such
inorganic molecules as N
2
O, CCl
4
, SF
6
, and organic molecules with halogen atoms. For
these additives, k
q
may be high while DE is low or negative [130,135]. Those molecules
were found to be good quenchers that were good electron scavengers in radiolysis [42].
This correlation suggests that electron transfer and energy transfer may have similar
mechanism, e.g.:
RH* B ! RH B* ! neutral products 30
RH* B ! RH
! neutral products 31
Reactions (30) and (31) may give the same products. In (31) the polarization energy
decreases the energy demand for temporal charge separation and it can be exothermic
when B has a considerable electron anity. For aromatic hydrocarbon quenchers (e.g.,
anthracene) such mechanism leads to dissipation of the excitation energy on the vibra-
tional levels. When the quencher molecules contain Cl or Br atom in the intermediate step,
Cl
or Br
elimination is expected, e.g., with benzyl chloride additive:

C
6
H
5
CH
2
Cl
! C
6
H
5
CH
.
2
Cl
32
As nal products of the transfer HCl, C
6
H
5
CH
3
, C
6
H
5
CH
2
-c-C
6
H
11
and (C
6
H
5
CH
2
)
2
were
found. The same products are expected in the electron-scavenging reaction [130].
3.2. Energy Transfer from Higher-Energy Excited States
The energy transfer from excited alkane molecules to 2,5-diphenyloxazole (PPO) was
frequently investigated, often with unusual results. For example, Kimura and Hormes
investigated the transfer using for excitation 3.310.5 eV photons from a synchrotron
source. They reported extremely eective energy transfer at energies 7.81 and 9.67 eV in
cyclohexane. The transfer at 7.81 eV was tentatively ascribed to energy transfer from the
eighth peak of the Rydberg series with a diameter of
f
3 nm (static quenching). They did
not observe similar ecient transfer in n-heptane [28]. Lipsky et al. also observed ecient
transfer in several saturated hydrocarbons at photon energy 7.7 eV. According to Wang
Figure 6 Energy transfer rate coecients from excited cyclohexane molecules to solutes as a
function of the DE energy dierence: (1) isooctane, (2) n-heptadecane, (3) cyclooctane, (4) trans-1,2-
dimethylcyclohexane, (5) isopropylcyclohexane, (6) cis-1,2-dimethylcyclohexane, (7) decalin, (8) 1-
decene, (9) 2-hexene, (10) tetramethylethylene, (11) benzene. (From Ref. 135.)
et al. [137] and Krishna and Lipsky [138], the transfer takes place from some unidentied
ion-pair state of alkanes.
4. FORMATION AND YIELD OF ALKANE EXCITED STATES IN RADIOLYSIS
The yield determined in a certain type of experiment usually strongly depends on the
assumptions made about the formation mechanism. In the older literature, the excited
molecules were often assumed to be produced solely in neutral excitations [127,139143]
and energy-transfer experiments with SternVolmer-type extrapolation (linear concen-
tration dependence) were used to derive G(S
1
). For instance, by sensitization of benzene
uorescence, Baxendale and Mayer established G(S
1
) = 0.3 for cyclohexane [141]. Later
Busi [140] corrected this value to G(S
1
) = 0.51 on the basis that in the transfer, in addition
to the uorescing benzene state S
1
, the S
2
and S
3
states also form and the S
2
!S
1
and
S
3
!S
1
conversion eciencies are smaller than 1. Johnson and Lipsky [144] reported an
eciency factor of 0.26 F 0.02 per encounter for sensitization of benzene uorescence via
energy transfer from cyclohexane. Using this eciency factor the corrected yield is G(S
1
)
= 1.15. Based on energy-transfer measurements Beck and Thomas estimated G(S
1
) = 1
for cyclohexane [145]. Relatively small G(S
1
) values were determined in energy-transfer
experiments for some other alkanes as well: n-hexane 1.4, n-heptane 1.1 [140], cyclo-
pentane 0.07 [142] and 0.12 [140], cyclooctane 0.07 [142] and 1.46 [140], methylcyclohexane
0.95, cis-decalin 0.26 [140], and cis/trans-decalin mixture 0.15 [142].
A basic problem of the energy-transfer experiments is that the quenchers used may
also react with electron or cationic species, in addition to the excited molecules. If the
excited molecules also form after charge recombination (which is now unambiguously
established), the quenchers may considerably hinder the formation of excited molecules
[8]. Comparison of the results obtained in this manner with those obtained via other
techniques shows that the solute technique strongly underestimates the G(S
1
) value. It
should be mentioned that in most of the sensitization experiments unrealistically high K
SternVolmer constants were obtained [141,142].
If the excited molecule formation is mainly because of electroncation recombina-
tion the concentration dependence of quenching of the precursor charged species may
follow some form of the modied WarmanAsmusSchuler (WAS) semiempirical equa-
tion [8], e.g.:
GScavenged S
1
precursor f
s
G
fi
G
gi
ac
n
1 ac
n

33
where n is usually taken as
1
2
(square-root concentration dependence). In the equation G
and G
gi
are the yields of free and geminate ions, respectively, and a is an adjustable
parameter characteristic to the scavenger. The fraction of S
1
excited molecules formed in
recombination, f
s
, can be smaller than 1 mainly because of three reasons:
1. Some of the cations may fragment or undergo ionmolecule reactions before
neutralization. As shown in the older literature, the fragmentation has higher
yield in the radiolysis of the smaller and/or highly branched alkanes such as
neopentane or isooctane. Ionmolecule reactions, such as the H transfer, may
also reduce the S
1
yield:
c-C
6
H
12
.
c-C
6
H
12
!c-C
6
H
13
c-C
6
H
11
.
34
The ionmolecule reactions and the spin eects (see below) were detailed in the
recent review of Shkrob et al. [7]; therefore, we only briey mention these
reactions.
2. As discussed earlier, the recombination is nearly completed within a few pico-
seconds; during this short time the spin correlation is maintained and from the
originally singlet geminate ion pair singlet excited molecule forms. However, if
several ion pairs are in each others vicinity (in the spur) there is a high probability
for cross-recombination. In cross-recombination in 3:1 ratio triplet and singlet
molecules form. In a very large spur in the limit statistically
1
4
of the recom-
binations give singlet product. The singlet fraction was calculated several times by
using experimentally derived spur-size distribution [8,146148]. Numerous
computer simulations were also made on the singlet/triplet formation probability:
the theoretical calculations predict singlet formation probabilities in the 0.50.7
range.
3. The singlet excited molecules formed in charge recombination may not convert
with 100% eciency to S
1
as discussed in Sec. 2.1. This eect may be important
for smaller molecules; for larger molecules such as the decalins or n-dodecane the
eciency is probably very close to unity.
The experimentally obtained f
s
values show larger divergence: based on alkane
uorescence measurement. Walter et al. [148] and Luthjens et al. [65,128] published 0.8
0.9. Later the latter authors modied their value to 0.65 [149]. In solutions of isooctane,
cyclohexane, or n-hexane with naphthalene, Sauer and Jonah established this value as 0.5
F 0.1; this singlet formation probability is approximately constant during the decay of
charged species up to 70 nsec [150]. In nal product experiments f
s
= 0.34 [151], 0.53, and
0.47 [84] was estimated for cyclohexane, cis-decalin, and trans-decalin, respectively. The
low value for cyclohexane is due to the ionic reactions before recombination.
Most papers published during the last 20 years on the formation mechanism of S
1
alkane molecules agree that they form mostly or nearly exclusively in charge recombina-
tion [65,72,73,128,148153]. In pulse radiolysis done with
f
50-psec pulses, denite after-
formation of uorescence was observed for the larger alkanes such as the decalins. In the
radiolysis of cyclohexane, Sauer et al. used electron scavenger in subnanosecond uo-
rescence measurements to determine the formation route. Because the charge scavenging
occurs on the time scale of geminate recombination (a few picoseconds), while the excited
molecule quenching takes place during the excited molecule decay (
f
1 nsec), they
separated these eects [153]. Based on the eective initial inhibition of excited molecule
formation they concluded that less than 10% of the S
1
excited cyclohexane molecules were
formed in direct excitation. Low direct excitation contributions were suggested also for
other alkanes [7,128,148].
The uncertainty about the formation mechanism is eliminated when such method is
used for the determination of the G(S
1
) value, which is invariant to the formation route.
Such method is the comparison of the yields of those products, which are formed only in
one way in the reaction of the S
1
molecules. Such products come from the singlet decay
channel: uorescence photons, products of H
2
or alkane elimination. The triplet channel
due to the large triplet yield originating from other processes than the S
1
!T
n
ISC (e.g.,
direct triplet excitation, or charge recombination with triplet product) cannot be used for
the calculation of the S
1
yield. The calculations are based on the equation:
GX UX GS
1
35
G(X) and U(X) are the Gvalue and the quantumyield of the product used for the calculation,
respectively. Two possible sources of errors should be mentioned. One is the energy
dependence of the photodecomposition. In order to obtain intrinsic yield U(X) should
be measured at photon energies as close as possible to the absorption onset, or appropriate
corrections should be used [154,155]. Both photon emission and photodecomposition
studies show that the energy dependence is more severe for the smaller molecules than for
the larger ones. Therefore, G(S
1
) for the larger molecules can be estimated with higher
accuracy. The second source of error is that X may not solely form in S
1
molecule trans-
formation.
The uorescence of liquid alkanes is supposed to originate entirely from the relaxed
S
1
state. Walter and Lipsky [154], by measuring the uorescence yields of alkane solutions
irradiated with 165 nm photons or
65
Kr beta particles (E
max
= 0.67 MeV) relative to
benzene uorescence, determined the following yields: 2.3-dimethylbutane G(S
1
) < 1.3,
cyclohexane 1.41.7, methylcyclohexane 1.92.2, dodecane 3.33.9, hexadecane 3.33.9,
cis-decalin 3.4, and bicyclohexyl 3.5. After reinvestigating the intrinsic quantum yield of
cyclohexane uorescence, Choi et al. published G(S
1
) = 1.45 for this alkane in Ref. 155.
For trans-decalin a G(S
1
) value of 2.83.1 has been accepted [65,128,132]. The uncertain-
ties in the values reect the uncertainties in the intrinsic uorescence quantum yields.
As discussed in Sec. 2.6, the characteristic singlet photodecomposition mode of n-
alkanes and cycloalkanes is the H
2
-molecule elimination (Table 4) with U(H
2
)
u
= 0.70.9.
This process has a high yield also in radiolysis [9193,111]. Based on experiments with
deuterated hydrocarbons, Fujisaki et al. [156] and Shida et al. [157] reported values of
G(H
2
)
u
= 1.4 and 1.6 for the yield of unimolecular H
2
detachment occurring in the
radiolysis of propane and n-butane liquids. In cyclohexane experiments with c-C
6
H
12
/c-
C
6
D
12
mixtures, Dyne and Jenkinson suggested that 1020% of the hydrogen yield of
G(H
2
) = 5.6 forms in unimolecular elimination [158]. Using the same technique Nevitt
and Remsberg [159] published G(H
2
)
u
V 1.4 for cyclohexane. The unimolecular H
2
elimination yields for a large group of alkanes were determined based on the alkene
and dimer yields using Eq. (10) [91,92,111,160]. Although this method of G(H
2
)
u
determination, because of the comparable alkene and dimer yields, is less accurate than
the calculation of U(H
2
)
u
, we think that the precision of the G(H
2
)
u
values in Table 4 are
better than F 15%. The accuracy of the G(S
1
) values calculated by using the U(H
2
)
u
and
G(H
2
)
u
yields and Eq. (35) is around F 20%. In some works H
2
elimination from the
alkane radical cations were also suggested [7,161]:
c-C
6
H
12
.
!c-C
6
H
10
.
H
2
36
However, the yields are probably very low, and for most compounds this reaction does not
change considerably the determination of the G(S
1
) values by the H
2
-elimination method
[7]. When interpreting the G(S
1
) values obtained by this method the possibility should also
be considered that besides S
1
states, to some extent, higher-energy excited states might also
contribute to the unimolecular H
2
elimination. This would cause the G(S
1
) data calculated
using this method to be higher than the real G(S
1
) values. Such an assumption would,
however, contradict the general observation that with increasing excitation energy and,
consequently, decreasing lifetime of the excited state, molecular processes lose their
importance and atomic and molecular processes become predominant [160]. The yield
determined by this method for cyclohexane, G(S
1
) = 1.41.7 [91,92,111,160], agrees with
the yield obtained in uorescence experiments.
In the case of alkanes with tertiary or quaternary carbon atoms the characteristic
decomposition mode is usually the fragment alkane elimination (Sec. 2.6) and its yield can be
used to estimate G(S
1
) values. Based on the fragment alkane elimination yield Pitchuozhkin
et al. [162] calculated a singlet G value of 3.3 F 1 for 2,2,4-trimethylpentane.
We collected the singlet yields determined by comparing the uorescence or product
yields measured in photolytic and radiolytic experiments in Fig. 7. The G value of low-
energy excited states is increasing with the size of the molecules. The trend is by no means
unexpected because the density of excited states is known to increase with the size of
molecules, giving rise to a more ecient internal conversion from the higher excited states
to the rst excited level, S
1
. The f
s
singlet fraction of the charge recombination may have
size dependence also due to the decreasing yield of ion decomposition with the molecular
weight of ions [160].
Figure 7 G(S
1
) value as a function of the carbon atom numbers in the molecules. When more than
one measured value was published, we tried to select the most probable value. Alkanes: (1) propane,
(2) n-butane, (3) n-pentane, (4) cyclopentane, (5) n-hexane, (6) cyclohexane, (7) n-heptane, (8)
cycloheptane, (9) methylcyclohexane, (10) n-octane, (11) cyclooctane, (12) isooctane, (13) n-decane,
(14) cyclodecane, (15) cis-decalin, (16) trans-decalin, (17) n-dodecane, (18) dicyclohexyl, (19) n-
hexadecane. (From Refs. 18, 29, 65, 92, 148, and 155.)
Under high-LET irradiation conditions by using uorescence detection [87,88] or
nal product measurements [102,163165], a continuous decrease of the S
1
alkane excited
molecule yields was detected with increasing LET. Holroyd et al. [87], in their soft x-ray
experiments, attributed this decrease to the fast quenching of excited molecules by radicals
in the spur. LaVerne and coworkers [102,163165] investigated the distribution of nal
product of cyclopentane, cyclohexane, and cyclooctane radiolysis in the presence and
absence of I
2
radical scavenger in a very wide LET range. They found that the proportion
of H-atom-forming reaction is increasing with increasing LET at the expense of other
hydrogen-forming reactions, e.g., H
2
molecule elimination. The shift was attributed to
changes in charge recombination from basically geminate recombination in low-LET
radiolysis to predominantly cross-recombination in high-LET heavy-ion radiolysis. In the
high-LET limit the S
1
yields were estimated as G c1.2, which is about one fourth of the G
= 45 ion pair yield.
5. THE ORIGIN OF STRUCTURE EFFECT IN ALKANE RADIOLYSIS
The products that form in photolysis and radiolysis of liquid alkanes at room temperature
can be divided more or less arbitrarily into two groups: products reecting primary CH
or primary CC ruptures. On this ground, one is able to calculate the U value or the G
value of molecules activated by the photon or ionizing radiation absorption and under-
going primary CH or CC bond scission [2,160]. There are several examples for the
calculation of the yields in Ref. 2. By investigating the low-LET radiolysis of about 30
alkanes the overall yield of these two processes was found to be approximately constant: G
= 6.5 F 1. The eect of chemical structure can be observed particularly in the ratio of the
competing primary CH and CC bond rupture reactions. This is obvious from Fig. 8a,
where the G(H
2
) values are displayed as a function of the G values of the primary CC
bond rupture reactions. In contrast to the decomposition of n-alkanes and cycloalkanes,
which yield mostly hydrogen and dehydrogenation products, some branched alkanes, e.g.,
neopentane and 2,2,4-trimethylpentane, decompose mainly by CC bond rupture.
In photolysis of liquid alkanes (Fig. 8b) the competition and structure eect are more
apparent than during radiolysis: the highly branched alkanes decompose nearly exclusively
by CC bond rupture. Since, during radiolysis of many alkanes, the decompositions
originating from low-energy excited states can make a signicant contribution (2555%)
to the nal product formation, and the reactions from this state show higher selectivity, a
considerable part of the structure eect and selectivity in radiolysis is due to the
decomposition of low-energy excited molecules. Another important source of the structure
Figure 8 Connection between primary CH and CC bond ruptures during radiolysis and
photolysis. Alkanes: (1) propane, (2) n-butane, (3) n-pentane, (4) n-hexane, (5) n-heptane, (6) n-
octane, (7) n-decane, (8) isobutane, (9) neopentane, (10) 3-methylpentane, (11) 2,2-dimethylbutane,
(12) isooctane, (13) cyclopentane, (14) cyclohexane, (15) cycloheptane, (16) cyclooctane, (17)
cyclodecane, (18) methylcyclopentane, (19) methylcyclohexane, (20) ethylcyclohexane, (21) 1,1-
dimethylcyclohexane, (22) cis-1,2-dimethylcyclohexane, (23) trans-1,2-dimethylcyclohexane, (24) cis-
1,3-dimethylcyclohexane, (25) trans-1,3-dimethylcyclohexane, (26) cis-1,4-dimethylcyclohexane, (27)
trans-1,4-dimethylcyclohexane. (From Refs. 18, 29, 91, 92, 99, 100, 108, 110, 111, 113, 114, and
160.)
eect is the ionic decomposition, which is eective for highly branched and especially
smaller molecular mass alkane radical cations. With most molecules these two types of
structure eects can act in the same direction: e.g., in the reaction of highly branched
alkanes both the ionic decomposition and S
1
decomposition result in high yield of CC
bond ruptures at the branched carbons. There is no agreement regarding the yields of ionic
decompositions, the yields for some molecules may be as high as G = 13.
It is obvious from this analysis that while the decompositions from the S
1
ex-
cited molecules or the radical cations tend to take place selectively, the bond ruptures
from other species, e.g., from higher-energy excited molecules are closer to a random
distribution.
Because of such diculties as the featureless absorption and emission spectra in the
vacuum ultraviolet region, very weak and energy-dependent uorescence intensity, short
excited-state lifetime, etc. the photophysics and photochemistry of alkanes is much less
known than those of other organic molecules, for instance, aromatic hydrocarbons. In this
chapter, the present status was reviewed.
At present there are dierent views about the nature of the alkane excited states. The
excited states are probably admixtures of Rydberg- and valence-type states. There are
some views that the initial energy absorption takes place in a basically Rydberg state and
than it relaxes to a valence-type excitation. The Rydberg-type excitations of alkanes have
valence type counterparts with the same symmetry [22]. According to some works the
lower-energy states are delocalized all over the molecules, while other works mention
strongly localized excited orbitals. Some excited-state properties may point to the localized
nature of the excited states. These include the characteristics of uorescence, the large
disparity between the absorption onset and the uorescence maximum (Stokes shift, D c
0.81.6 eV, width of the uorescence peak (r
f
c 1 eV), and also the molecular structure
dependence of these characteristics, e.g., the very strong and characteristic inuence of the
alkane chain branching and the high probability of decompositions at the tertiary and
quaternary carbons. In the photoexcitation of many alkanes the uorescence quantum
yields decrease with increasing photon energy; this dependence is attributed to an energy-
dependent relaxation of the higher excited states to the relaxed S
1
state from where the
uorescence occurs.
The excited-state lifetimes (s c 1 nsec) determined by uorescence decay, absorb-
ance decay, or steady-state quenching experiments after single-photon, multiphoton, or
ionizing radiation excitation generally agree indicating that the same excited state (the
relaxed S
1
) is observed in all experiments. Within a homologous series, e.g., for the n-
alkanes, s is increasing with the size of the molecules, similarly to the uorescence in-
tensity. The ratio of the two quantities, R = U
f
/s, the so-called radiative rate coecient,
within a group of compounds remains constant: R c1.6 10
6
sec
1
for n-alkanes,
f
2
10
5
sec
1
for linear methylalkanes,
f
5.3 10
6
sec
1
for vicinally branched dimethylal-
kanes,
f
8 10
6
sec
1
for cyclohexanes, and
f
1.2 10
7
sec
1
for dimethylcyclohexanes.
The lifetimes in the group of the so-called nonuorescing alkanes (geminally substituted
alkanes, C
5
, C
7
C
10
cycloalkanes) are short (s V 0.3 nsec): the absence of uorescence may
have two causes, low radiative rate coecient and fast chemical decay.
The radiationless S
1
!S
0
transition has a negligible role in the depopulation of the
excited molecules; the process, which competes with the weak uorescence (
f
1%) is the
chemical decomposition (
f
99%). Two basic chemical decomposition types are distin-
guished: hydrogen molecule and alkane molecule elimination (in these reactions no
intermediate radicals are observed) and CH or CC scission yielding two radicals or
CC scission yielding a biradical (in the reaction of cycloalkanes).
The decomposition of a C
n
H
2n+2
alkane molecule to H
2
molecule and C
n
H
2n
alkene
molecule belongs to the rst class of reactions. This is the typical decomposition mode of
the S
1
excited n-alkanes and C
5
C
10
cycloalkanes at room temperature. The quantum yield
of the reaction decreases with decreasing temperature. Thus, it needs some thermal
activation. The reaction is attributed to an S
1
!S
x
-type IC process; S
x
denotes some
singlet state that gives the products. The elimination takes place mostly or probably
entirely from a single carbon atom yielding an H
2
molecule and a carbene intermediate.
The carbene, by intramolecular 1,2-H atom shift, rearranges to an olen. In the cases of
C
7
C
10
cycloalkanes the carbene may also stabilize in the form of cross-bridged bicy-
cloalkanes by 1,3-, 1,5-, or 1,6-H atom shifts.
Alkane elimination is a basic photodecomposition mode of highly branched alkanes,
e.g., most of the excited neopentane molecules split directly to methane and isobutene.
The radical-forming reactions are suggested to take place mostly after an S
1
!T
n
type ISC: the reactions have nonactivated character. The homolytic split to H atom and
alkyl radical has a considerable yield in the photolysis of n-alkanes and cycloalkanes, while
the scission to two radicals is characteristic of the decay of excited branched alkane
molecules.
With the increase of the photon energy used for excitation, the yield of the radical-
forming reactions increases, whereas that of the H
2
elimination decreases.
By now it is unambiguously established that the energy transfer from the S
1
excited
alkane molecules takes place with a diusional mechanism at the contact distance: the
reaction radii deduced from such experiments (0.8 F0.2 nm) practically agree with the sum
of the radii of the reacting molecules. In some special cases, however, very fast energy
transfer was also observed (e.g., to PPOmolecules): the fast transfer was attributed to energy
transfer from high-orbit Rydberg excited states or from some unspecied ion-pair state.
The properties of the alkane triplet states are much less known than the properties of
the singlet states. It seems there is a dissociative, and thereby short-living triplet state
f
1
eV below the lowest singlet excited state [29]. The other triplet states are probably also
dissociative. The low-lying and long-living triplet states, supposed in some works based on
unusual energy-transfer results, still needs real experimental verication [7].
In radiolysis most of the S
1
excited molecules (up to 90%) form in charge
recombination. The singlet fraction, f
s
, based on the newer experimental and theoretical
studies is around 0.50.7. Both theoretical and experimental work indicate that f
s
decreases with increasing LET value of radiation, because of preferred cross-recombina-
tion and by preferred triplet formation in the high ionizing density tracks.
The frequency of CH and CC bond ruptures in the radiolysis of liquid alkanes is
far from a statistical distribution, and there is a correlation between the dissociation
reactions and the chemical structure. In contrast to the decomposition of n-alkanes and
C
5
C
10
cycloalkanes, which yield mostly hydrogen and dehydrogenation products, some
branched alkanes, e.g., neopentane and 2,2,4-trimethylpentane, decompose mainly by C
C bond rupture. The considerable structure eect can to some extent be traced back to the
fact that with many alkanes 25% to 55% of the total primary decomposition of G = 6.5 F
1 occurs from low-energy singlet excited states. Chemical reactions from these states tend
to take place selectively, whereas the bond ruptures from higher-energy states are closer to
a random distribution. Fragmentation of the highly branched and especially smaller
molecular mass alkane radical cations can also contribute signicantly to observed
selectivity of bond ruptures in radiolysis.
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14
Radiation Chemical Effects of Heavy Ions
Jay A. LaVerne
1. INTRODUCTION
The chemical eects induced by the passage of heavy ions in matter have been actively
examined for more than 100 years. Curie and Debierne in 1901 performed the rst radia-
tion chemistry study on water by any type of radiation using a-particles from solutions
of radium salts [1]. All of the early studies examined the production of gases, mainly
hydrogen, from radium solutions [29]. Radium was used because of its availability, but
equally important is the reality that products could not be observed using other types
of radiation because of impurities and the crude techniques of the time. In contrast to the
observable transitions in radium solutions, Fricke could detect no decomposition of pure,
air-free water by x-rays as late as 1933 [10]. Many of the transient species discussed in the
preceding chapters of this book were just being discovered at about this time and a com-
plete description of the observed chemical eects was understandably dicult. However,
experimental techniques quickly advanced and many early monographs on radiation eects
note the dierent eects observed with heavy ions compared to that found with fast elec-
trons, x-rays or g-rays [1116].
A wide variety of early experimental [17] and theoretical studies [1822] have formed
much of the basis for understanding the chemical eects of heavy ions. The general con-
cepts of heavy ion radiolysis have not changed since these studies. However, more informa-
tion on specic systems is constantly being accumulated, especially in complicated mixtures
and in heterogeneous systems. The details of heavy ion radiolysis will not be discussed in
depth, but rather an overview of the major eects and the reason for their occurrence will be
given here. An examination of rare events specic to heavy ion radiolysis can be found in a
recent review [23]. Descriptions of typical experimental techniques used in heavy ion
radiolysis are published elsewhere [24,25]. The discussion in this chapter will be limited to
the radiolysis of water because most of the work has been performed in this medium and
because of the importance of water in a variety of applications. Many of the fundamental
ideas discussed here for liquid water are applicable to other liquids. However, the nature of
the processes occurring in many solids and almost all gases may lead to very dierent eects
than discussed here.
In addition to the fundamental scientic aspects, many studies on the chemical eects
of heavy ion radiolysis have signicant practical applications. These applications range
from the nuclear power industry [26,27], space radiation eects [28], medical therapy [29],
and the environmental management of radioactive waste materials [30]. Much of the future
eort on the examination of heavy ion radiolysis will driven by these need-based demands.
The complexity of such systems can be overwhelming and good fundamental research on
simple systems is required.
The term heavy ions usually refers to any ionizing radiation other than fast elec-
trons. In this chapter, the term will apply to charged atomic nuclei of all the elements from
protons to uranium ions. The concepts presented may apply to other particles such as
muons; however, a number of collision parameters are dierent between these ions and
atomic nuclei and one should refer to specic monographs for details. High velocity molec-
ular ions fragment in the rst few collision processes and one gets atomic nuclei of the
same velocity, which can then be treated as individual heavy ions. Neutrons, being neutral,
are not classied as heavy ions either. They produce recoil ions in passing through matter.
The recoil ions, oxygen or hydrogen in water, are usually formed with a wide energy dis-
tribution and each ion can be examined independently.
2. ENERGY LOSS PROPERTIES OF HEAVY IONS
Most radiation chemical studies involve ions with initial energy of a few MeV or more. At
these energies, the main interaction responsible for energy loss is the Coulombic force
between the charge of the incident heavy ion and that of the electrons of the medium. Energy
transferred from one of these collisions leads to excitation or ionization of the medium
molecule and the rate at which this energy is lost per unit path length, dE/dx, is called the
electronic stopping power of the medium. Rutherford was the rst to successfully explain
the scattering of charged particles using Coulombic forces and classical mechanics [31].
Bohr applied this cross section using an impact parameter approach to determine the stop-
ping power and ranges of ions in matter [32]. A quantum mechanical theory of stopping
powers was later developed by Bethe based on energy and momentum transfer [33]. Both
the Bohr and Bethe formalisms are equally valid depending on the charge and velocity of
the incident heavy ion [34]. Almost all other methods for determining the energy loss by
charged particles through electronic processes are modications of these two early theories
and a complete discussion is given in Chapter 2 of this book.
The details of the stopping power equations have been very well summarized else-
where [22,3438]. Most applications involve ions of low charge and high velocity in which
the Bethe formalism is valid. The nonrelativistic stopping power equation of Bethe for
heavy ions is given approximately by,
dE=dx
4pe
4
Z
2
N
mV
2
ln
2mV
2
I

1
where e and m are the charge and mass of the electron, Z and V are the charge and velocity
of the incident particle, and N and I are the electron density and mean excitation potential
of the medium. Relativistic terms, shell eects, the Fermi density correction, and other
modications to the stopping power are usually added to the logarithmic term as needed.
Sometimes stopping powers are further subdivided into hard and soft [32] or glancing and
knock-on [22] collisions. One can also encounter restricted stopping powers in which an
upper limit is placed on the energy loss in a given collision [39]. These distinctions are
made according to the energy loss in the collision and aided in the early development of
track structure as described below. However, such distinctions are rarely necessary for
understanding basic radiation chemistry. They can also lead to erroneous assumptions
because the energy cuto is often arbitrary.
Equation (1) is rarely used in its given form to determine stopping powers or ranges
of ions. There are too many diculties in estimating the eective charge of the incident
ion, screening eects, eective mean excitation potentials, and other factors that must be
taken into account for accurate stopping powers. Most investigators use standard com-
pilations that employ semi-empirical ts to experimental data [4042]. The compilations
typically compare the stopping of dierent ions in the same target medium and scale to
other media or standardize the stopping of protons in dierent media and scale to other
ions. The accuracy of the compilations is thereby increased considerably. However, the
predictions of these compilations should be veried for the specic radiolytic condition to
be examined as some compilations are more accurate than others for a particular ion in a
given energy range. Ref. 42 is developing into the standard compilation for most heavy ion
studies, while Ref. 41 is especially suitable for very high Z particles.
Low-energy, high Z particles may also have a sizable nuclear stopping power due to
elastic nuclearnuclear interactions [4042]. These processes can be thought of as billiard-
ball type collisions between the nucleus of the incident ion and the nuclei of the atoms
making up the medium molecules. These collisions occur at very low energies and can
usually be ignored, e.g., nuclear stopping equals electronic stopping for carbon ions in water
at energy of about 20 keV. On the other hand, the nuclear component can be considerable
with high Z particles and should be included in range or stopping power determinations,
e.g., nuclear stopping equals electronic stopping for uranium ions in water at energy of
about 3.5 MeV. However, no specic chemistry of water radiolysis has been identied un-
equivocally to the nuclear stopping, so it will not be treated separately. The nuclear stopping
power is not to be confused with nuclear fragmentation. The latter process occurs at very
high energies and leads to fragmentation of the incident heavy ion.
General trends of the stopping power can be easily deduced from Eq. (1). The veloc-
ity term in the numerator of the logarithmic term and in the denominator of the pre-
logarithmic term gives rise to the familiar Bragg peak, i.e., with decreasing velocity of the
incident particle the stopping power increases to a maximum and then decreases at lower
velocities. Specically, the Bragg peak refers to the increase in ionization toward the end
of the particle track since he rst noticed this eect in the ionization of gases [43]. How-
ever, the expression is also commonly used in reference to the stopping power. The dis-
tinction is negligible in water because ionization is the dominant outcome due to energy
loss by the incident heavy ion. The stopping powers of water for ve dierent ions are shown
in Fig. 1 as a function of incident energy [42]. Also shown in this gure is the stopping power
for fast electrons [44]. The important aspect of the stopping powers is the huge dierence
between heavy ions and electrons. Heavy ion stopping powers are typically several orders of
magnitude higher than that for fast electrons. There are two major consequences due to the
high rate of energy loss for heavy ions that aects the radiation chemistry: the very short
range and the track structure.
The dotted lines in Fig. 1 show the stopping powers for the dierent ions at a
constant velocity in units of MeV/amu. This unit of energy is very often used in heavy ion
radiolysis and it is based on the classical formula for kinetic energy, E =
1
2
MV
2
, where M
is the heavy ion mass. As seen in Eq. (1), the ion velocity is a dominant parameter in
energy loss processes and the MeV/amu energy unit is more convenient to use than con-
verting to absolute velocity units. Remember that MeV/amu is actually proportional to
the square of the velocity.
There are several methods used to describe the range of an energetic heavy ion. The
penetration, projected range, or depth refers to the mean displacement in the initial di-
rection of motion and is the most commonly used parameter in radiation chemistry.
Scattering will always add a radial component to the trajectory, but the magnitude of this
component is usually small for ions of energies typically used in radiation chemistry ex-
periments. Therefore the range of heavy ions often can be determined from the continuous
slowing down approximation, csda, by the following equation.
R
csda

Z
E
o
0
dE= dE=dx 2
where E
o
is the initial energy, and the stopping power, dE/dx, is obtained from one of the
compilations. Fig. 2 shows the ranges corresponding to the ions in Fig. 1. The extremely
short ranges make experiments with heavy ions dicult. A 1-MeV electron has a range of
about 4 mm in water and experiments are relatively easy to conduct. On the other hand, a
1-MeV proton has a range of only 24 Am. Window materials and sample thickness become
major concerns at these ranges. A proton would need about 20 MeV of energy to have the
same range as a 1-MeV electron, and other heavier ions would need considerably higher
energy. The ranges given in Fig. 2 are csda ranges and somewhat over estimate the true
penetration. Applications requiring greater accuracy should use Monte Carlo simulations
of heavy ion trajectories. However, these simulations require detailed knowledge of the
elastic cross sections, which are not known for heavy ions in many materials. In practice,
the csda ranges are usually sucient for the determination of penetration, but the true
range should always be checked experimentally.
The electronic stopping power involves a collision between the heavy ion nucleus and
an electron of the medium. The reduced mass of the encounter can always be assumed to
Figure 1 Stopping power, dE/dx, of some heavy ions [42] and electrons [44] in water as a function
of energy. The dotted lines show the stopping power for heavy ions of equal velocity.
be equivalent to that of the electron, even with incident protons. Therefore energy loss
depends on the velocity and not the mass of the incident ion. In other words, there are
really no isotope eects for radiolysis with ions of the same element, provided they have
the same velocity. For example, protons and deuterons of equal velocity give similar
radiation chemical yields [45]. Subtle mass eects on the stopping power of heavy ions
are predicted in more detailed theories [35,46], but their eects are small and have not yet
been observed in normal water radiolysis.
The charge and velocity of the incident particle are important parameters in the
characterization of energy loss processes as predicted by Eq. (1). The velocity can usually
be obtained by energy or time of ight analysis, but the charge is more dicult to deter-
mine [4749]. It is obvious from Eq. (1) that for two ions of the same velocity but with
dierent charges, e.g., He
+1
and He
+2
, the ion with twice the charge will have four times
the stopping power. Experiments with gas targets show the expected dependence of the
cross section on the charge of the incident particle [50]. However, in gases one is dealing
with a single isolated collision. The rates of capture and loss of electrons in condensed
media are very rapid and the heavy ion attains an equilibrium charge state depending on
its velocity [5153]. Strictly, each individual heavy ion has an integral charge, but the
probability of nding that charge state depends on the velocity. However, an average
charge per heavy ion is often used in place of Z in stopping power formulas such as Eq. (1).
Experimental studies have led to several empirical equations for the average eective
charge, Z
e
, of heavy ions. The following formula is accurate over a wide energy range of
greater than 0.3 MeV/amu [48,49].
Z
e
=Z
o
1 exp 6:35 v=Z
4=3
o

1=2

3
Figure 2 Range, csda, of some heavy ions [42] and electrons [44] in water as a function of energy.
The dotted lines show the range for heavy ions of equal velocity.
The energy, v, is in units of MeV/amu and Z
o
is the heavy ion atomic number. This for-
mula assumes that a proton at the same energy is completely stripped and should not be
used at energy less than 0.3 MeV/amu. Corrections can be applied to extend Eq. (3) to
lower energies [48]. Fig. 3 shows the relative eective charge for several heavy ions as a
function of their energy. It can be seen that the lighter ions are generally stripped at ener-
gies above 1 MeV/amu. The core electrons of heavy nuclei are tightly bound and con-
siderably more energy is required to strip them in a collision process.
Energy loss due to charge exchange processes and the equilibrium charge are in-
cluded in the total stopping power found in compilations. This energy does not have to be
considered explicitly. There have been several references to track end eects that are
presumably due to charge exchange or other processes occurring at the end of the heavy
ion track. Schuler [54] once suggested that the excess production of molecular hydrogen
in benzene is due to charge exchange processes. However, later calculations using more
reliable cross sections indicate that charge exchange processes are insucient to explain all
of the hydrogen produced [55]. No other chemistry has been shown to be due exclusively
to charge exchange processes.
3. FUNDAMENTALS OF TRACK STRUCTURE
Many of the observed radiation chemical eects in water are due to the geometry of the
physical energy deposition events, commonly referred to as the track structure. The obser-
vation that the energy absorbed in the medium was more important for determining the
resultant chemistry than the energy loss by the incident particle was rst proposed by
Zirkle et al. who coined the term linear energy transfer, LET, to indicate this signicance
[56]. Of course, the track structure is largely determined by the energy loss processes.
Linear energy transfer is usually assumed to be equivalent to the stopping power of the
Figure 3 Relative eective charge of some heavy ions in water as a function of incident energy
(Eq. (3)). The dotted lines show the relative eective charge for heavy ions of equal velocity.
medium, which is almost always valid for bulk liquid water. However, one should use
caution in heterogeneous systems or in isolated nanometer sites. Track structure eects
are commonly called LET eects because most of the early studies used this parameter
to characterize the dierent yields for the various heavy ions. Linear energy transfer has
continued to be a dominant parameter in the radiation chemistry of heavy ions, but even
in the earliest studies it was apparent that LET was not the only factor that determined
product yields [57,58]. The variation in product yields for two ions at the same LET was
correctly ascribed by early investigators to subtle dierences in the track structures [16,
57,58].
The medium absorbing the energy loss by the ionizing radiation is almost always
structured. Water is made up of nite dimensioned molecules. Stopping power formulas
such as Eq. (1) give average rates of energy loss to a continuum of bound electrons with no
regard to the molecularity of the medium. In normal systems, energy is lost by the incident
radiation in stochastic processes leading to isolated regions or clusters of excited states and
ion pairs of medium molecules. The early cloud chamber pictures of Wilson in the 1920s
[59,60] show that h-particle tracks are made up of well-separated ionization events, except
near the end of the tracks. The cloud chamber tracks of a-particles appear as solid,
continuous strings of ionization events. Theories developed in the 1940s and 1950s used
these visualizations as aids to describe radiation chemical events due to the nonhomoge-
neous distributions of reactive species [12,61,62].
The track structure is determined to a large extent by the distribution of energy ab-
sorption by the medium, which is well characterized by the dipole oscillator strength
distribution, f(e). Classically, the dipole oscillator strength distribution gives the number
of electrons of the medium capable of absorbing a photon of energy e. The complete inte-
gral of the dipole oscillator strength distribution over all energies is equal to the total num-
ber of electrons in a molecule, ZV. Phase eects and other characteristics of the medium
are included in the dipole oscillator strength distribution. A large number of molecules,
even in the dierent phases, have distributions comparable to that for liquid water as
shown in Fig. 4 [63]. Therefore the overall track structures of ionizing radiation in most
liquid media are similar. Subtle dierences will be found because the oscillator strength
distributions are not identical for all media and other mechanisms, such as channeling in
crystals, may have a signicant contribution. The density of the medium has a direct eect
on energy loss processes, which is the reason why there is little meaning of track structure
in the gas phase.
The dipole oscillator strength distribution does not directly correlate to energy loss
by charged particles. However, Monte Carlo simulations of ionizing radiation using cross
sections incorporating the dipole oscillator strength distribution can give this information
[63,64]. Fig. 4 shows the frequency of a given energy loss for 1-MeV electrons in liquid
water. The similarity between the energy loss distribution and the dipole oscillator strength
distribution is obvious with both showing peaks at about 20 eV. There is a wide range of
possible collisions due to the passage of a fast electron in water, but it can be seen from
Fig. 4 that the most probable events involve energy losses of less than 100 eV.
The mean energy loss by a fast electron in liquid water is about 60 eV and somewhat
independent of the phase and the initial electron energy [63,64]. Collisions involving this
magnitude of energy loss will produce secondary electrons that further lead to an average
of one or two ionizations [65]. Low-energy electrons have relatively large total elastic cross
sections with a substantial backscattering component [6668]. In other words, electrons of
a few tens of eV do not go very far in liquid water and show a nearly isotropic angular
distribution as they thermalize [69]. The electrons will thermalize and eventually become
hydrated, adding another spatial delocalization from the initial energy loss event. The net
result is that the initial energy loss event leads to a cluster, or spur, of two or three ion-
izations spatially localized. The concept of a spur in the liquid phase of water is very old
[61,62]. The existence of spurs in water manifests itself in the characteristic time depen-
dence of the decay of reactive species produced by water decomposition [70]. The spur is
still the main entity used by radiation chemists to explain kinetic eects with low LET
radiation. Solvation of the electron does not occur in the gas phase and the delocalization
of the electron during this process makes up a substantial fraction of the size of the spur.
The spur has no counterpart in the gas phase, which causes much confusion when applying
gas phase theory and cross sections to the liquid phase.
Following the initial ionization events, water decomposes within a few picoseconds
to give a spur composed of hydrated electrons, OH radicals, H atoms, H
2
, and H
2
O
2
[16].
The nonhomogeneous distribution of water decomposition products making up the spur
relaxes by diusion and reaction of the sibling radicals and molecules. A combination of
direct observations of the hydrated electron decay with model calculations can be used to
estimate the average geometry of the spur [71]. Obviously, each spur is slightly dierent.
However, even a single 1-MeV electron produces greater than 10
4
spurs so that its chem-
istry appears as an average over all spurs. Time decay measurements using low-energy
multiphoton ionization just above the ionization potential of water have also been used to
estimate the distribution of low-energy electrons in water [72]. These latter experiments
agree well with the predicted results for the typical spur produced by fast electrons. The
observed time decay of the hydrated electron coupled with Monte Carlo calculations
suggests that the typical spur in electron radiolysis is well approximated by a Gaussian
distribution with a characteristic radius of 45 nm [73].
The average energy loss per unit track length of a 1-MeV electron is about 0.2 eV/nm
[64]. With an average energy loss per collision event of 60 eV the mean separation of spurs
is 300 nm, which is much too far apart for interspur reactions. (It is assumed throughout
Figure 4 Relative dipole oscillator strength distribution, f(e), for liquid water [63] and frequency of
a given energy loss by 1-MeV electrons in liquid water [64].
this article that incident particles are isolated from each other, an assumption not neces-
sarily correct at very high dose rates or with very short pulses of intense beams.) On the
other hand, a 5-keV electron has an average LET of 3 eV/nm, which corresponds to an
initial average separation of only a few spur diameters. The spurs produced by an electron
of this energy are not initially overlapping, but they will overlap soon thereafter as they
develop in time. The resulting geometry leads to a short track as originally dened by
Mozumder and Magee [20]. These authors suggested that even lower energy electrons
form blobs, which are elliptical or stretched spurs. All of these geometric shapes are meant
to be aids in predicting the resultant chemistry and should not be considered as xed
entities of nite dimensions.
The tracks of heavy ions can be explained in much the same fashion as that for fast
electrons, e.g., considering the primary energy loss followed by the delocalization due to
the multiple secondary electron thermalization and solvation. If the LET is greater than 3
eV/nm the spurs will be formed overlapping or will overlap shortly thereafter. At LET
much less than 3 eV/nm the spurs will exist independently of each other and the observed
chemistry of a heavy ion should be much like that of a fast electron. Monte Carlo simu-
lations suggest that the energy loss distributions for high velocity heavy ions are very
similar to that for fast electrons, i.e., the frequency of a given energy loss for a heavy ion is
nearly the same as shown in Fig. 4 for fast electrons (S.M. Pimblott, unpublished results).
Collisions by heavy ions have slightly dierent kinematic parameters than fast electrons.
For instance, an electron can lose up to half its energy in a collision, whereas the maximum
energy loss by a heavy ion is 4mE/M, where m is the electron mass, and E and M are the
heavy ion energy and mass, respectively. For both electrons and heavy ions, the energy
loss is largely determined by the dipole oscillator strength distribution, which is signi-
cantly peaked at low energy. The result is that almost all types of ionizing radiation pro-
duce large amounts of low-energy electrons with distributions in water similar to that
shown in Fig. 4. However, the initial collision process strongly determines the track struc-
ture and resultant chemistry because it determines the spacing of the clusters of low-energy
electrons.
Recent studies have applied Monte Carlo techniques well established for electrons to
heavy ions [74]. The predicted density normalized mean free path, K, of several heavy ions
is given in Fig. 5. It can be seen that the mean free path mirrors the stopping power by
decreasing with decreasing energy and passing through a minimum at low energies. Spur
sizes can vary widely, but from the discussion above a typical spur can be assumed to have
a diameter of about 10 nm. Fig. 5 shows the relationship between a spur diameter and the
mean free path of several ions. Low-energy heavy ions will produce primary ionization
events well within the diameter of a spur. Spatial delocalization due to thermalization and
solvation of the secondary electrons will result in one continuous track with a columnar-
like structure. Experimentally it has been observed that radical and molecular yields with
protons above about 20 MeV, 3 eV/nm, are virtually the same as with fast electrons
[75,76]. This observation agrees well with predictions based on the mean free path shown
in Fig. 5. Even higher energies are required for a helium or carbon ion track to resemble
that of a fast electron. These expected trends are observed experimentally, as will be shown
below. It has been speculated that the charge on an ion may slightly alter the distribution
of species within the spur [77], but no such process has been conrmed experimentally.
For a given medium such as water, its density and the velocity of the incident heavy
ion contribute to the formation of the columnar track structure. The spacing of the pri-
mary energy loss events must be within the delocalization of the secondary electrons for
eects attributed to high LET to occur. For this reason, typical LET eects will not be
observed in the gas phase. Simple density scaling of experimental or theoretical data
between the gas and condensed phases should be performed with caution.
Fig. 5 shows that the mean free path of low-energy carbon ions is less than that of a
water molecular diameter. Calculations based on such short mean free paths may predict
two energy loss events within the same molecule. However, as discussed elsewhere in this
book, the double ionization cross section is much lower than predicted by these results.
The problem is that cross sections are normally based on a single isolated collision at
gaseous density. Extrapolation to the condensed phase can lead to unrealistic predictions.
The column of species dened by the overlapping spurs along the path of a high
LET particle makes up what is commonly referred to as the track core [21]. Its physical
parameters are dicult to quantify and it has no corresponding entity in the gas phase.
Obviously, some energy loss collisions will be violent enough to form true y-rays, i.e., sec-
ondary electrons with enough energy to make tracks of their own. Various attempts have
been made to separate the track core from the region of radiation eects due to secondary
electrons (a region sometimes called the penumbra) [21,22,78,79]. There are at least two
problems with such an attempt. First, there is no clear demarcation between the two regions,
either by energy or chemically. The result has been confusion and dierent core denitions
for various chemical systems. A second diculty in dening a track core, or any track
parameter, is that the track is dynamic. The track is constantly expanding in time due to
diusion of the transient species and reactions initially associated with the track core may
envelop those due to the secondary electrons. Despite the inherent problems, some radiation
chemical problems have been successfully addressed by treating each part of the track sepa-
rately [7983]. This approach to heavy ion track modeling is advantageous because of
its relative simplicity. However, Monte Carlo calculations are required to completely eluci-
date the track structure and resulting chemistry. The few published Monte Carlo studies on
heavy ions are quite promising [74,84,85].
Figure 5 Energy dependence of the density normalized mean free path for e
,
1
H,
4
He, and
12
C
ions in liquid water. The dotted line shows the water diameter and the dashed line shows the typical
spur diameter. (From Ref. 74.)
4. CHEMICAL EFFECTS OF TRACK STRUCTURE
This section will discuss general eects due to track structure that apply to most condensed
phases. Water radiolysis will be used in specic examples because more data exist for this
chemical system than any other. As discussed above, the earliest experiments showed that
there were dierences in product yields for various ionizing radiations in liquid water.
With increasing particle LET there is an increase in the yields of molecular products such
as H
2
and H
2
O
2
and a corresponding decrease in the yields of radicals such as e
aq
, H, and
OH [16,86]. The nonhomogeneous distribution of reactive species initially produced by the
energy deposition relaxes in time toward a homogeneous distribution. In pure water, a
competition is quickly established between radicalradical combination reactions among
the sibling radicals and radical diusion into the bulk medium. Increasing the particle LET
increases the probability of radicalradical combination reactions with a corresponding
increase in molecular products.
It has always been assumed that the initial decomposition of water is independent
of particle type [8789]. There are experimental results that seem to support this con-
clusion. Pulsed experiments with protons nd that the short time yield of the hydrated
electron is similar to that found with fast electrons [90,91]. In addition, W-values, the aver-
age energy required per ion pair, for high-energy particles in a given medium are nearly
independent of the particle type [92]. Ion pairs are the main initial species formed in the
radiolytic decomposition of water so one would expect similar yields for the products due
to these species. In special circumstances the initial product yield may be dependent on a
particle type, e.g., low-energy heavy ions with large contributions from nuclear scattering
processes or radiation with a high probability of causing multiple ionization of the medium
molecules. For the most part, observed variations in product yields of a given medium with
radiation type or energy are due to eects of track structure on the radiation chemistry.
There are a few important details that must be addressed in discussing product yields
with heavy ions because of their extremely short range. For example, a 10-MeV proton
(LET = 4.7 eV/nm) has a range in water of 1.2 mm while a 10-MeV carbon ion (LET = 700
eV/nm) has a range of 13 Am. Both particles would be completely stopped in the solution
in most practical applications. The chemistry measured in such a conguration is an aver-
age over all particle energies from the incident particle energy, E
o
, to zero. Radiation
chemical yields, G-values, are given as the number of molecules formed or lost per 100 eV
deposited, and track segment yields, G
i
, are the radiation chemical yields in a discrete seg-
ment of path length. Within this small path segment the energy, LET, and other param-
eters of the heavy ion are well dened and constant. Model calculations normally predict
track segment yields while experiments usually, but not always, give track average yields,
G
o
. The dierence between track average and track segment yields can sometimes be sig-
nicant. The denition of the track segment yield is G
i
=d( G
o
E
o
)/dE
o
= G
o
+E
o
dG
o
/dE
o
.
It can be seen that track segment yields approach track average yields as the initial par-
ticle energy approaches zero or if the track average yield is independent of energy. Track
segment yields are often equivalent to track average yields, but such equality should not
be assumed.
Fig. 6 shows a plot of G
o
E
o
for HO
2
production as a function of the initial energy
of protons [75]. The proton was completely stopped in all the experiments and the track
average yield of HO
2
measured. The traditional integral or track averaged G-value at
10 MeV is given by the slope of the solid line to be 0.030 molecules/100 eV. The dier-
ential or track segment yield at 10 MeV is given by the slope of the dotted line to be
0.023 molecules/100 eV. This 30% dierence can be signicant in some applications. As
the proton energy approaches zero, the two types of yields approach each other. However,
one must remember that the Bragg peak occurs at the lower energies and yields are not
expected to be the same on both sides of it. There is as yet no satisfactory way to deal with
this problem. The best technique for obtaining dierential yields is to t the data as pre-
sented in Fig. 6 and determine the derivative [75]. However, one needs accurate yield
measurements at appropriate energy intervals, data which are seldom available.
There is a considerable amount of eort required to experimentally measure the
energy dependence of product yields. One solution is to use high energies where the long
ranges allow the direct measurement of track segment yields. However, nuclear frag-
mentation also occurs at high energies, which complicates interpretation of the data. The
track average yields are often the only measured values, especially in the early literature.
Track segment yields are often presented as a function of LET, especially when comparing
the results for dierent types of ions. The correctness of using LET will be discussed later,
but it is denitely incorrect to couple track average G-values with track segment LET. The
track average LET is dened as 1=E
o
m
E
o
0
dE=dx dE, which correctly weighs the LET
over the entire track. This method of representation of the data is by far the most common
encountered in the literature.
Product yields with heavy ions are generally presented as a function of the dier-
ential or integral LET of the irradiating particle depending on the type of G-value. How-
ever, LET is not the sole parameter that describes the track structure and thereby the
observed yields [16,57,58]. Many experimental observations have shown that for two inci-
dent particles at the same LET radical yields are greater and molecular yields are lower for
the ion with a higher charge [57,58,77,93]. Fig. 7 shows an example of the LET eect on the
production of HO
2
and O
2
in the radiolysis of water [75,9496]. The experiments actually
convert HO
2
to O
2
so both are measured, but HO
2
is the dominant species. Although HO
2
is a radical, it behaves like a molecular species as its yield increases with increasing LET.
Figure 6 The production of HO
2
in the proton radiolysis of water as a function of initial ion
energy [75]. The slope of the solid line (0.030) is the track average yield while the slope of the dotted
line (0.023) is the track segment yield for 10-MeV protons.
Many of the expected track eects discussed above are observable with this system. For
instance, high-energy protons give about the same HO
2
yield as fast electrons because they
both deposit energy in isolated spurs. One can readily observe that LET is not a unique
parameter for describing yields.
Equation (1) predicts to a rst approximation that for two dierent types of particles
to have the same LET the one with the higher charge will have a higher velocity. A higher
incident particle velocity produces a larger radial distribution of energy deposition in part
because the distribution of secondary electrons increases with an increase in the heavy
ion velocity. Several theoretical studies have examined the average radial distribution of
energy about a heavy ion track and the results agree with the observations [21,22,79,97,98].
Although two heavy ions may deposit the same amount of energy per unit path length the
ion with higher charge will lose that energy in a larger volume, which leads to a less dense
track of reactive species. Dierent media and even dierent products in a given media can
exhibit a variety of dependencies on particle Z at a given LET.
Early studies on biological media suggested that there must be a better parameter
than LET for characterizing the response to heavy ions [99]. These observations led to the
proposal that Z
2
/b
2
would be a better parameter, where b is the ratio of the ion velocity to
the speed of light [100]. The rationale for such a parameter is that the radial energy dis-
tribution should be related to the maximum energy of the secondary electron, which is
proportional to b
2
or E/M. Equation (1) suggests that the rate of energy loss along the
particle path is proportional to Z
2
times the corresponding value for a proton of the same
velocity. Combining the estimates for radial and axial energy loss gives a rst approx-
imation to the energy density for nonrelativistic ions as Z
2
/b
2
. At very low energies, the
parameter Z should be replaced by the eective charge of the heavy ion, Z
e
, as discussed
above and given by Eq. (3). Several sets of radiation chemical data have been examined
Figure 7 Track average yields of HO
2
as a function of heavy ion LET: (n,E,.)
1
H,
4
He, and
12
C,
Ref. 75; (o)
12
C, Ref. 94; (O)
12
C, Ref. 96; (+)
58
Ni, Ref. 95. The dotted line is the limiting fast
electron yield of 0.02 [123].
with some success using this parameter [101104]. However, it was also pointed out that
this parameter does not work in some instances [102]. Monte Carlo techniques have been
applied to heavy ion tracks in liquid water in order to examine energy loss in detail [74].
Fig. 8 shows the results from that work for the radial energy density or the fraction of
energy loss as a function of the radial distance. The radial distributions of energy about
protons and helium ions are found to be similar for ions of equal velocity, but not for
equal LET [74]. The results also show that the response of the Fricke dosimeter more
Figure 8 Radial energy deposition rate and fraction of total energy loss in a track segment as a
function of radial distance for (solid line) 1 MeV
1
H and for
4
He ions of (oooo) equal velocity and
() equal LET. (From Ref. 74.)
closely follows the parameter MZ
2
/E than LET. This parameter is equivalent to Z
2
/b
2
but
easier to visualize from common units used to describe heavy ions. The next section will
show that the MZ
2
/E parameter gives nearly universal agreement for all track average
product yields of water radiolysis at long times.
The eects of track structure on product yields are often discussed in terms of one
parameter or another that is related to the energy loss of the heavy ion. This approach
implies a static track, which is not true. There is a tremendous amount of diusion and
reaction of reactive species following the energy loss processes. One of the biggest chal-
lenges for experimentalists and theoreticians is determining the temporal history of prod-
ucts in water radiolysis with heavy ions. Not only do the time dependencies put severe
limitations on track models but also they can be vital for predicting radiation damage in
concentrated systems that cannot be probed directly. Several pulsed heavy ion experiments
have directly measured water product yields at specic times [90,91,105113]. Except for
the work of Burns and coworkers who used water jets, these experiments are limited to
determining the product yields on the microsecond time domain. The major diculty with
pulsed experiments is the need for relatively large doses in narrow pulses and the very
short heavy ion range. These limitations restrict the number of systems that can be exam-
ined and the time scales. Competition kinetics can be used to determine the time scale of
chemical reactions at high LET where direct observations are not possible. Solutes that are
radical scavengers will stop the competition between radical reaction and diusion at a
time characteristic of the particular scavenging reaction. By changing the solute concen-
tration one can eectively probe the chemistry in the particle track at dierent times.
Even most of the pulsed experiments rely on scavengers to stop the chemistry at short
times so product yields can be observed with pulses at longer times. Several experiments
using scavenger techniques have been able to determine the temporal variation of radicals
and molecular products from nanoseconds to microseconds using a variety of heavy ions
[114118]. Considerably more work is required to obtain a complete set of data for all
products of water radiolysis.
5. HEAVY ION RADIOLYSIS OF WATER
The only true method to characterize a product yield in the radiolysis of water is to have the
complete temporal dependence for a particular heavy ion with a given energy. The track is
constantly evolving in time due to diusion and reaction of the reactive species and in many
instances the yields are never really constant. This result is very dierent than fast electron
or g-radiolysis where the yields of transients can be considered to be invariant with time
from a few microseconds to milliseconds or longer. Track processes are occurring at times
less than a microsecond, while homogeneous reactions begin to dominate after a few min-
utes and products approach steady-state concentrations. The transition from track pro-
cesses to homogeneous chemistry occurs quickly with heavy ions. It is sometimes dicult
to consider the yield of a product as a single valued entity.
Product yields in the radiolysis of water are required for a number of practical and
fundamental reasons. Model calculations require consistent sets of data to use as bench-
marks in their accuracy. These models essentially trace the chemistry from the passage of
the incident heavy ion to a specied point in time. Engineering and other applications often
need product yields to predict radiation damage at long times. Consistent sets of both the
oxidizing and reducing species produced in water are especially important to have in order
to maintain material balance. Finally, it is impossible to measure the yields of all water
products for every heavy ion and energy. Therefore one must to be able to interpolate to
other ions or energy for which no data exist.
The next few subsections will present data for the products in the radiolysis of water
with a wide variety of heavy ions. Product yields with heavy ions are rarely constant in time,
but most of them vary slowly in the microsecond region. Furthermore, most chemical
systems used to probe yields with heavy ions were developed for examining fast electron or
g-radiolysis in the microsecond region. The following discussion on product yields can be
assumed to apply to the microsecond time regime. Because a wide range of systems are used
to determine product yields, consistency between the dierent experiments can be obtained
by examination of the material balance. The net decomposition of water can be obtained by
setting the number of H atoms in each product equal to the number of H atoms in the net
water decomposed to form that product and similarly for O atoms [16].
2GH
2
O 2GH
2
Ge
aq
GH GHO
2
2GH
2
O
2
GOH 4
GH
2
O 2GH
2
O
2
GOH 2GHO
2
2GO
2
5
Combining these two equations gives the material balance between the oxidizing and
reducing species formed in the decomposition of water.
2GH
2
Ge
aq
GH 2GH
2
O
2
GOH 3GHO
2
4GO
2
6
Molecular oxygen formation is probably negligible at all but the highest LET and HO
2
can
be normally ignored with fast electrons and g-rays.
The discussion in the previous section suggests that the track of a heavy ion becomes
more like that of a fast electron with increasing velocity. Therefore one expects that in the
high velocity limit the yields of water products with heavy ions are the same as with fast
electrons or g-rays. The yields for the major products of water radiolysis in fast electron or
g-radiolysis are given in Table 1. These values were taken froma number of dierent sources
in conjunction with the results predicted by model calculations [73,116,119123]. Material
balance shows that almost four molecules of water are decomposed for every 100 eV of
energy absorbed by fast electrons or g-rays. Because only about six water molecules are
initially decomposed, most of the water products escape intraspur reactions in fast electron
or g-radiolysis.
Linear energy transfer has often been shown to be a poor parameter for character-
izing product yields. Therefore in order to compare the results for the dierent ions the
MZ
2
/E parameter has been used. This parameter has been successfully used in the past and
seems to work well for the data presented here. Note that an increase in MZ
2
/Ecorresponds
to an increase in LET so product trends as a function of MZ
2
/E presented here are
comparable to similar discussions in the literature using LET. Unfortunately, there is no
good formalism to t product yields as a function of MZ
2
/E. The solid lines in Figs. 914
Table 1 Product Yields in the Radiolysis of Water at about 1 Asec
Particle e
aq
H
2
H OH H
2
O
2
HO
2
H
2
O
Fast electron/g
(reference)
2.5
(73, 119)
0.45
(120)
0.56
(119, 121)
2.5
(73, 122)
0.70
(116)
0.02
(123)
3.94
1 MeV
1
H 0.48 0.94 0.31 0.67 0.91 0.06 2.61
5 MeV
4
He 0.26 1.12 0.12 0.38 0.95 0.10 2.48
l 0.12 2.02 0.0 0.0 0.97 0.56 3.06
Figure 10 Track average yields of H
2
as a function of MZ
2
/E: (n)
1
H,
4
He, Ref. 121; (x)
4
He,
7
Li,
Ref. 26; (.)
1
H,
4
He, Ref. 131; (o)
1
H,
4
He,
14
N,
20
Ne, Ref. 126; (5)
1
H,
4
He, Ref. 45; (+)
1
H, Ref.
127;()
14
N, Ref. 128; (1) , Ref. 129. The dotted line is the limiting fast electron yield of 0.45 [120].
The dashed lines are for 1 MeV
1
H and 5 MeV
4
He ions.
Figure 9 Track average yields of e
aq
as a function of MZ
2
/E: (n)
1
H,
4
He, Ref. 121; (x)
4
He,
7
Li,
Ref. 26; (.)
4
He, Ref. 115; (D)
10
B(n,a)
7
Li, Ref. 124; (5)
10
B(n,a)
7
Li, Ref. 125; (+,)
58
Ni,
238
U, Ref.
93. The dotted line is the limiting fast electron yield of 2.5 [73,119]. The dashed lines are for 1 MeV
1
H and 5 MeV
4
He ions.
Figure 12 Track average yields of OH radical as a function of MZ
2
/E: (x)
4
He,
7
Li, Ref. 26; (.)
4
He, Ref. 114; (.)
1
H,
12
C, LaVerne, unpublished results; (o)
1
H,
4
He,
14
N,
20
Ne, Ref. 126; (5)
1
H,
4
He, Ref. 45. The dotted line is the limiting fast electron yield of 2.5 [73,122]. The dashed lines are for
1 MeV
1
H and 5 MeV
4
He ions.
Figure 11 Track average yields of H atom as a function of MZ
2
/E: (n)
1
H,
4
He, Ref. 121; (x)
4
He,
7
Li, Ref. 26. The dotted line is the limiting fast electron yield of 0.56 [119,121]. The dashed lines are
for 1 MeV
1
H and 5 MeV
4
He ions.
Figure 13 Track average yields of H
2
O
2
as a function of MZ
2
/E: (n)
1
H,
4
He, Ref. 132; (x)
4
He,
7
Li, Ref. 26; (.)
1
H,
4
He,
12
C, Ref. 116; (o)
1
H,
4
He,
14
N,
20
Ne, Ref. 126; (5)
1
H,
4
He, Ref. 45; (1)
, Ref. 133. The dotted line is the limiting fast electron yield of 0.7 [116]. The dashed lines are for 1
MeV
1
H and 5 MeV
4
He ions.
Figure 14 Track average yields of HO
2
and O
2
as a function of MZ
2
/E: (.)
1
H,
4
He,
12
C, Ref. 75;
(o)
12
C, Ref. 94; (O)
12
C, Ref. 96; (+)
58
Ni, Ref. 95; (j)
1
H,
4
He,
14
N,
20
Ne, Ref. 126; (D)
1
H,
4
He,
Ref. 121; (+) , Ref. 133. The dotted line is the limiting fast electron yield of 0.02 [123]. The dashed
lines are for 1 MeV
1
H and 5 MeV
4
He ions.
were obtained by tting the data for each product Y to the function G( Y) = G
e
( Y) +
( G
l
( Y)G
e
( Y))(ax)
n
/(1 + (ax)
n
), where x is MZ
2
/E, a and n are tting parameters, and
G
e
and G
l
are fast electron and innite MZ
2
/E (LET) yields, respectively. This function
works well in the inection region where most of the data are found, but its approach to the
limiting values is not good. Therefore the values of the parameters a and n will not be given,
but the value of n generally varied from 0.4 to 1.4.
5.1. Hydrated Electron
Hydrated electrons have been widely studied in fast electron radiolysis using pulsed
techniques. Only a few pulse radiolysis studies have examined hydrated electron formation
with heavy ions [90,81]. Burns and coworkers used 3-MeV protons and reported yields out
to 70 nsec, which is too short to compare to the results with solutes [90]. The work of Nale-
way et al. measured track segment yields in the microsecond region using time resolved
techniques [81]. Track segment yields were also measured by Appleby and coworkers [103].
All of the yields for the hydrated electron presented in Fig. 9 are track average yields
obtained in scavenging experiments [26,115,121,124,125]. Nitrous oxide and nitrate are
most often used as scavengers of the hydrated electron. Fig. 9 shows that there is good
agreement for hydrated electron yields over a wide range of MZ
2
/E values. The major
deviation occurs for the
10
B(n,a)
7
Li recoil experiments [124,125]. An average value of MZ
2
/
E for the two recoils is used, which is probably giving too high a value. Dosimetry is
sometimes a problem in the use of recoil ions.
Hydrated electron yields decrease with increasing MZ
2
/E, but they do not seem to
decrease to zero. Experiments have been performed on aerated and deaerated Fricke
dosimeter solutions using
58
Ni and
238
U ions [93]. One half of the dierence in the ferric
ion yields of these two systems is equal to the H atom yield. The Fricke dosimeter is highly
acidic so the electrons are converted to H atoms and to a rst approximation the initial
H atom yield can be assumed to be zero (see below). There is considerable scatter in the
data of the very heavy ions, but they seem to indicate that hydrated electron yields de-
crease to a lower limit of about 0.1 electron/100 eV. The hydrated electron distribution is
wider than that of the other water products because of the delocalization due to solvation.
This dispersion probably allows some hydrated electrons to escape the heavy ion track at
even the highest value of MZ
2
/E.
5.2. Molecular Hydrogen
The yields of H
2
are usually straightforward to measure using gas detection techniques. A
small amount of scavenger is added to stop the OH radical back reaction from occurring,
which would decrease the yields. Fig. 10 shows the results for H
2
as a function of MZ
2
/E for
the various ions [26,45,121,126130]. A track segment yield was determined at very high
energies, but not included in the gure [131]. There is some scatter in the data, but the overall
agreement is good. Molecular hydrogen yields are extremely sensitive to the scavenging
capacity of system because this species evolves over a long period of time [130]. The
scavenging capacity is equal to the product of the scavenger concentration and the
scavenging reaction rate coecient and reects the time dependence of H
2
formation. Fur-
ther detailed experiments on the H
2
yield at dierent scavenging capacity will probably help
clarify the results.
As expected, the H
2
yield increases with increasing MZ
2
/Evalues. Measurements with
ssion fragments found a limiting yield of 2.0 H
2
molecules/100 eV [129]. The maximum
value of MZ
2
/E with ssion fragments was determined from the average velocity and
eective charge of the two main fragments. Although the ssion fragment data point may
be in some error because of dosimetry, a t of data suggests that the maximum H
2
yield
is about 2 molecules/100 eV. These results show that H
2
is the major product of water
radiolysis at high MZ
2
/E values.
5.3. Hydrogen Atom
Only two studies have determined H atom yields in neutral water with heavy ions [26,121].
H atom yields are extremely dicult to determine directly because of competition with
hydrated electrons or OH radicals. Yields of H atoms are usually estimated from dier-
ences in molecular hydrogen yields using various scavengers for the H atom. Fig. 11 gives
the H atom yields as a function of MZ
2
/E. There are not many data points, but they seem
to agree with each other and show a decrease with increasing MZ
2
/E values.
The measured H atom G-value is about 0.25 at MZ
2
/E = 1, while the equivalent
yield of hydrated electrons is found at MZ
2
/E = 10. The persistence of the hydrated
electron to higher MZ
2
/E values suggests that it does not decrease to zero at an innite
value of MZ
2
/E. Most H atoms are produced in conjunction with OH radicals in the core
of the heavy ion track. The recombination rate constant is high so there is a small prob-
ability that H atoms will escape the track at high LET (MZ
2
/E). H atoms can be formed
by hydrated electron reactions and their yield cannot decrease to zero if hydrated electron
yields do not. However, hydrated electron yields are low at high MZ
2
/E values so the H
atom yield can be considered negligible in this region.
5.4. Hydroxyl Radical
OH radical yields have been measured over a wide range of energy and particle type and
the results are shown in Fig. 12 [26,45,102,114,126]. There is generally good agreement
with the data considering that the OH radical is dicult to measure. Most studies use
formate or formic acid to give CO
2
, while others rely on material balance. There are always
experimental problems with H atom reactions contributing to the observed product yields.
Intratrack combination reactions cause the OH radical yields to decrease with in-
creasing MZ
2
/E values from a G-value of 2.5 with fast electrons and g-rays. The lower
limit of OH radical yield appears to be zero for high MZ
2
/E values. OH radicals are highly
reactive and they are formed in the center of the heavy ion track so it is not surprising
that there is little probability for them to escape the track. The results also suggest that
OH radical production reactions, e.g., H atom reaction with H
2
O
2
, are negligible at high
MZ
2
/E values.
5.5. Hydrogen Peroxide
Fig. 13 gives the results of several studies on the measurement of H
2
O
2
with heavy ions
[26,45,116,126,132,133]. The yield of H
2
O
2
never varies signicantly from its value with
fast electrons and g-rays. There is a signicant amount of scatter in the data so predicting
trends is dicult. Large scatter in the data is expected for yields determined by material
balance or other manipulation of two or more sets of measurements. However, the pro-
duction of H
2
O
2
is usually determined directly using spectroscopic techniques. Hydrogen
peroxide is fairly reactive with all the radical species produced in water radiolysis. The
production of H
2
O
2
is due to OH radical combination reactions, but the yields are sen-
sitive to added scavengers for all radicals. Even variations in the concentration of hydrated
electron scavengers have been shown to aect H
2
O
2
yields [134]. This sensitivity to the
particular radiolysis conditions makes comparison of dierent sets of data dicult.
Some studies have suggested that H
2
O
2
yields reach a maximum corresponding to
the LET of 5-MeV helium ions and then decrease with increasing LET [116]. The decrease
was thought to be due to OH radical reactions with H
2
O
2
in the dense tracks at high LET.
Experiments with ssion fragments suggest that the H
2
O
2
yield does not decrease to zero
at very high MZ
2
/E values [133]. The latter result was obtained in acidic solutions, but the
outcome should be somewhat similar for neutral solutions. If this assumption is valid, then
the limiting value of H
2
O
2
at high MZ
2
/E values is about 1 molecule/100 eV, which is not
signicantly dierent from the value of 0.7 found with fast electrons and g-rays. It should
be stressed that the small variation in H
2
O
2
yields with the MZ
2
/E parameter is due to
multiple compensating reactions and not due to its inertness.
5.6. Perhydroxyl Radical
The mechanism for the production of HO
2
is probably the most uncertain in water
radiolysis. Its yield is extremely small with fast electrons and gamma rays, but HO
2
is the
most abundant radical produced at high LET. A wide variety of studies have determined
HO
2
yields over a huge range of MZ
2
/E values as shown in Fig. 14 [75,9496,121,126,133].
The data agree very well, which is expected because all the sources used ferrous sulfate
cuprous sulfate aqueous solutions. Cuprous sulfate is reduced in this system by the HO
2
to
give O
2
, which is then measured by a variety of gaseous techniques. However, O
2
produced
directly or by track reactions is also determined using this technique. Therefore the yields
generally quoted for HO
2
also include O
2
. Molecular oxygen yield is expected to be low at
all but the highest MZ
2
/E values.
The yield of HO
2
seems to increase to a value of over 0.5 molecule/100 eV at high
MZ
2
/E values. Extrapolation of the present data suggests a maximum value of 0.56, which
agrees well with the measured value of 0.5 with ssion fragments [133]. A previous work
estimated 0.57 molecules/100 eV for the track segment yield of HO
2
at innite LET. The
limiting values agree well with each other. If HO
2
has a simple precursor, such as the O
atom, then the limiting value of HO
2
at high MZ
2
/E values represents the yield of this
precursor in the initial decomposition of water. Further experimental and model studies
are necessary to separate the relative yields of HO
2
and O
2
and the mechanisms for their
formation.
5.7. Protons and Helium Ions
Many applications of heavy ion radiolysis involve a-particles or neutrons. The former are
well represented by the results for 5-MeV helium ions while the latter mainly give protons
with a distribution of energy. (Neutrons will also produce low-energy oxygen ion recoils in
water.) For the sake of comparison in this work, 1-MeV protons are assumed to represent
neutron yields. Individual G-values at other proton energies can be determined from
Figs. 914 and used in specic applications involving well described energy distributions.
Each of the gures (Figs. 914) has dashed lines showing the corresponding MZ
2
/E values
for 1-MeV protons and 5-MeV helium ions.
Table 1 contains the tabulated G-values for water products estimated for 1-MeV
protons and 5-MeV helium ions. The data are consistent with the curves in Figs. 914 and
give material balance between the oxidizing and reducing species. The major uncertainties
are in the yields for H
2
O
2
because of the large amount of scatter in the data for this
product. Net water decomposition yields determined from the data of Table 1 and Eq. (5)
show a net decrease from fast electrons to 1-MeV protons to 5-MeV helium ions. The
increasing density of reactive species in the tracks of these particles leads to a net recom-
bination of water. However, the net water decomposition seems to increase at the highest
MZ
2
/E values. The decreased yields of radicals at high MZ
2
/E values allow the molecular
products to survive the intratrack reactions and diuse into the bulk. About half of the
initial water decomposed by heavy ions is not recovered on the microsecond time scale.
6. FUTURE
Time resolved and track segment yields are important for fundamental studies on water
radiolysis with heavy ions. Advances in accelerators and laser probe systems will make
direct time resolved measurements easier. Scavenger concentration studies for obtaining
time dependencies will remain the most common experimental heavy ion technique.
Scavenger systems are amendable to track segment yield determination and the use of
older nonpulsed accelerators. Some products such as molecular hydrogen may never be
determined using time resolved techniques. Second-order reactions in the high-density
regions of heavy ion tracks may be a problem with some solutes. However, there is con-
siderable condence in the use of some of the systems that have been examined thoroughly.
New systems are constantly being evaluated and developed. All of the studies probing the
fundamental water products will be invaluable in predicting radiation damage in unex-
amined systems and for the development of track models. Detailed Monte Carlo track codes
for the radiation chemistry in heavy ion tracks must be advanced beyond the present level.
Much of the future work on heavy ion radiolysis will be largely driven by practical
applications. Corrosion processes associated with nuclear reactors and waste storage
containers will be a popular area of research because of the impact to society and the
availability of funds [11,132]. Scavenger and temperature eects on the main oxidizing
species involved in corrosion, e.g., H
2
O
2
, will be examined for application to the cooling
water in nuclear reactors. Cosmic studies, especially those related to planetary evolution,
will require extensive examination of the radical reactions in ices. Health eects ranging
from space travel, evaluation of the hazards of radon, and medical therapy will dominate
much of the work on water with biological endpoints. A large amount of work will be
performed on water in heterogeneous situations, such as absorbed water or bulk water
near solid surfaces. The interfacial eects are especially challenging because of the
dierences in initial energy distribution and in the type of radiolysis products formed.
ACKNOWLEDGMENTS
The research described herein was supported by the Oce of Basic Energy Sciences of the
U.S. Department of Energy. This document is NDRL-4424 from the Notre Dame Radia-
tion Laboratory.
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15
DNA Damage Dictates the Biological
Consequences of Ionizing Irradiation:
The Chemical Pathways
William A. Bernhard
University of Rochester, Rochester, New York, U.S.A.
David M. Close
East Tennessee State University, Johnson City, Tennessee, U.S.A.
1. BIOLOGICAL CONSEQUENCES OF EXPOSURE TO IONIZING
RADIATION
1.1. Cellular Endpoint
The eects of ionizing radiation on DNA have been studied for many years because of the
central role the DNA plays as the major cellular target. Cell killing, mutagenesis, and
transformation are all caused by damage to DNA.
The ability of external penetrating ionizing radiation to cause biological damage was
recognized soon after the discovery of x-rays in 1896. Radiation protection standards for
workers were introduced in the 1920s. These rst standards were based on the ability of
ionizing radiation to produce acute eects such as erythema and could be observed im-
mediately after exposure. At the same time, the appearance of cancers among radiation
workers showed that radiation could produce neoplastic eects. This led to the recogni-
tion of long-term epidemiological studies for understanding radiation risks and setting
standards.
1.2. DNA is the Critical Target
When ionizing radiation aects just one nucleotide in a sequence, this may produce a point
mutation. Most point mutations are of little consequence because the same protein or a
functional variation is made anyway. However, some point mutations result in a nonsense
message from which a nonfunctional protein is constructed, while other point mutations
give a meaningful but changed message leading to a protein with altered properties.
Radiation can also cause larger-scale errors involving many nucleotides. In some
cases, the change in the chromosome is visible with a microscope (called chromosome
aberrations). Some important types of chromosome aberrations are deletions, amplica-
tion, and translocation. Deletions are simply loss of a segment of DNAwith the consequence
that a number of dierent proteins, coded by the deleted region, are not made at all. This
kind of error is thought to occur in the childhood cancer retinoblastoma. The amplication
type of error, with repetition of a whole sequence of DNA bases, also occurs in some child-
hood cancers. Translocation is what happens when one piece of DNA is physically moved
and joined onto some unrelated piece of DNA. Some kinds of human leukemia may result
from this type of error.
One eect of complex DNA damage is a cell unable to produce copies of itself. This is
called reproductive death; the cell can no longer divide. In tissue, a very large number of cells
will be present, so death of a few cells makes little dierence to the function of the tissue. If
the radiation dose is increased, some signicant eects may occur quickly. In humans, such
eects include radiation sickness, skin burns, or failure of blood cell production. For each of
these eects to be large enough to be noticeable, a minimum radiation dose, or threshold,
has to be exceeded. For all doses above this, the severity of the eect becomes greater with
increasing dose. These are nonstochastic or deterministic eects.
Some radiation eects result from nonlethal damage to a single cell. These eects are
called stochastic. They have the property that there is no threshold for these eects to
occur. It is the probability of occurrence rather than its severity which increases with dose.
The causation of some cancers may be rooted in a stochastic eect.
The dose from low-LET (linear energy transfer) ionizing radiation is delivered by
high-speed electrons (Compton and photoelectrons) traveling through the cell and creating
primary ionization tracks. One track of ionizations is the minimum disturbance at the
cellular level. Paretzke [1] has shown how one can convert the energy of an x-ray or a g-ray
into electrons and their distribution. One can then determine how many photons of a given
energy are required to deposit a given dose. Tables are available which present tissue dose in
centi-Gray (cGy) when the average track rate per cell nucleus is 1. For example, there would
be, on average, one track per cell nucleus for a dose of 1.0 Gy from a medical x-ray. The
same would be true for a dose of 0.33 Gy from
137
Cs.
Some radiobiologists believe that cancer can be initiated as a result of a single
radiation track passing through a single cell nucleus. That would mean cancer induction
can be a unicellular process following the rules of chance. This could be taken to imply that
there is no safe dose or no safe dose rate. Of course, most DNA damage is corrected by
repair enzymes. So a key question then becomes this: does repair of carcinogenic injuries
operate awlessly when dose is suciently low? If every carcinogenic lesion to DNA was
faithfully repaired, then the net eect of a particular dose to cancer induction would be
zero. It follows then that many small doses, with corresponding times in between, could be
absorbed without increasing the cancer rate. Human epidemiological studies show that
repair fails to prevent radiation-induced cancer, even at doses where the repair system has
ample time to deal with only a few tracks at a time. Therefore, a question of considerable
current interest is whether or not there is an inherent inability of the repair system to x
certain types of complex damage to DNA.
1.3. Unique Characteristic of Radiation Damage
DNA damage is caused routinely, and frequently, by normal endogenous biochemistry.
This type of damage is restricted to single sites and therefore to a single strand. Damage to a
single strand is relatively easy to faithfully repair since the complementary strand is avail-
able as a template. Radiation damage to DNA is very dierent since much of the damage is
produced in clusters; one example of which are the double-strand breaks (dsb). Double-
strand breaks pose a greater risk of misrepair. A dsb can lead to loss of base sequence
information or can permit the two ends of a break to separate and rejoin with the wrong
partner. Therefore the repair of dsb is essential in preventing chromosomal fragmentation,
translocations, and deletions.
1.4. Genomic Instability
The Low Dose/Low-Dose Rate Conundrum
The current health risks associated with exposure to low-dose radiation are extrapolated
fromhigh-dose data taken fromthe Life Span Study of the Japanese atomic bomb survivors.
Currently, a linear no threshold extrapolation is recommended. The numerous technical
reports and scientic papers about the Japanese A-bomb survivors were widely interpreted
as showing that the eects of occupational exposures to radiation would be too small to
detect in epidemiological studies. However, questions about the reliability of the A-bomb
results were presented by Stewart and Kneale [2]. Their Oxford Childhood Study observed
that children whose in utero exposures were as little as 10 to 20 mSv had 40% more
childhood leukemias than those who were not exposed. No similar eects are reported in the
A-bomb data. Of course, the nding of no eect is not a compelling argument for or
against a safe dose.
During World War II, a dierent exposure situation was created in the United States
by the Manhattan Project. Several hundreds of thousands of workers were recruited to a
new industry in remote and secret locations. Since some of the hazards of working with
radiation were recognized in advance, workers at many sites were monitored for radiation
exposure. A new discipline, Health Physics, was created to provide radiological protection.
The systematic collection of dosimetry records created an opportunity to investigate
relationships between repeated exposure to small doses of radiation and disease.
Studies of nuclear workers have suggested that radiation risk estimates based on A-
bomb survivors could be underestimating the cancer risks fromextended low-level exposure
to radiation [3]. Due to such studies, and advances in our understanding of basic mech-
anisms in radiation biology, the importance of determining the consequences of low dose/
low dose rate exposure has become more apparent. The BEIR (Biological Eects of
Ionizing Radiation) VII Committee is currently evaluating new DOE Low-Dose Radiation
studies (http://lowdose.tricity.wsu.edu/). The current protection standard used by the
International Commission of Radiation Protection is 20 mSv whole body annual dose
equivalent; in the United States, 50 mSv per year is used.
Bystander Eect
Acentral tenet in radiation studies has been that energy must be deposited in a cell nucleus to
elicit a biological eect. Now, a number of nontargeted eects of radiation exposure have
been described which suggest that one must reevaluate this central tenet. One of these
nontargeted eects is the bystander eect, which describes the ability of the cell aected by
radiation to induce instability in neighboring cells that have not absorbed any radiation
energy. Convincing demonstrations of the bystander eect have come from studies using
charged particle microbeams.
Using the Columbia microbeam, Zhou et al. [4] passed one alpha particle through the
nuclei of mammalian cells. When 10% of the cells were irradiated with a single alpha
particle, the mutation yield was similar to that observed when 100% of the cells were
irradiated. Clearly, a single alpha particle can induce genomic instability in cells that were
not irradiated.
Hormesis
Working in the opposite direction of the bystander eect is hormesis, which is the stim-
ulation of a protective eect by small doses of radiation. It has been proposed that a low
priming dose may increase the number or quality of enzymes available to repair
subsequent radiation damage. But to date the underlying biochemical basis of hormesis
is not known. In addition, it is not clear how to extrapolate the information gained from
studies of lower organisms to humans. UNSCEAR (United Nation Scientic Committee
on the Eects of Atomic Radiation) [5] examined the notion of adaptive response in
1993 and concluded that while it was an interesting phenomenon that occurs in some cell
systems at various stages of development, it has little relevance in radiation protection.
While it seems likely that the biochemical trigger for hormesis is damage to the DNA, this
is not yet proven.
2. ENERGY DEPOSITION
2.1. Ionization and Excitation
Most of the energy associated with an incident x-ray or g-ray is absorbed by ejected
electrons. These secondary electrons are ejected with sucient energy to cause further
ionizations or excitations. The consequences of excitations may not represent permanent
change, as the molecule may just return to the ground state by emission or may dissipate
the excess energy by radiationless decay. In the gas phase, excitations often lead to
molecular dissociations. In condensed matter, new relaxation pathways combined with the
cage eect greatly curtail permanent dissociation. Specically in DNA, it is known that the
quantum yields for uorescence are very small and relaxation is very fast [6]. For these
reasons, the present emphasis will be on the eects of ionizations.
The initial chemical events involving the deposition of energy in DNA are conven-
iently divided into two parts: (1) energy deposited in water and (2) energy deposited in the
DNA itself. These are often called indirect and direct eects. Since some of the water in a
cell is intimately associated with the DNA, these terms must be used with caution. The
presence of DNA close to an energy deposition event in the water will eect the fate of the
species produced, and, likewise, water molecules closely surrounding the energy deposition
event in the DNA will modify the subsequent fate of the initial species. So the presence of
each component modies the behavior of the other.
2.2. Indirect Effects
The initial ionization of a water molecule produces an electron and the water radical
cation. The water radical cation is a strong acid and rapidly loses a proton to the nearest
available water molecule to produce an HO
.
radical and H
3
O
+
. The electron will lose
energy by causing further ionizations and excitations until it solvates (to produce the
solvated electron e
aq
). In addition to the two radical species HO

.
and e
aq
, a smaller
quantity of H-atoms, H
2
O
2
, and H
2
are also produced.
Of the two radical species HO
.
and e
aq
, the hydroxyl radical is more important in the

radiation chemistry of DNA. The e
aq
adds selectively to the DNA bases. The radiation

chemistry of the DNA base radical anions is discussed in Sec. 3. The one-electron reduced
bases are viewed as less important in the overall scheme since they do not lead to strand
breaks [7].
About 20% of the HO
.
radicals interact with the sugar phosphate by H-atom
abstractionandabout 80%react by additiontothe nucleobases. Inmodel sugar compounds,
the Habstraction would occur evenly between the hydrogens on C1V, C2V, C3V, C4V, and C5V. In
DNA, Habstraction occurs mainly at C4V , since the C4VHis in the minor groove and to some
extent with the C5VH
2
.
The HO
.
radical is electrophilic and can interact by addition with the unsaturated
bonds of the nucleobases. For the pyrimidines, this would be the C5jC6 double bond [8,9].
For the purines, this would include predominately C4 and C8 addition, with a minor amount
of C5 addition [10,11].
2.3. Direct Effect
Since there is such an imprecise division between direct and indirect eects in the literature,
some experimental results are presented to clarify this classication. Basically, one cannot
detect HO
.
radicals at low DNA hydrations (ca. 10 water molecules per nucleotide) [12].
This means that in the rst step of ionization, the hole produced in the DNA hydration
shell transfers to the DNA. It is impossible to distinguish the products from the hole
or electron initially formed in the water from the direct-eect damage products. For this
discussion, direct-type damage will be considered to arise from direct ionization of
DNA or from the transfer of electrons and holes from the DNA solvation shell to the
DNA itself.
2.4. Direct-Type vs. Indirect-Type Damage
The DNA solvation shell consists of about 2022 water molecules per nucleotide; of these,
f
1517 waters associate with the nucleoside and
f
5 waters associate with the phosphate
group [13,14]. Water outside the solvation layer is termed bulk water. Upon freezing,
the DNA solvation water forms two primary phases: the ice phase, consisting of one or
more of the crystalline forms of ice, and a DNA-associated phase, consisting of ordered
water which comes in direct contact with the DNA (primary layer) and disordered water in
the secondary layer. DNA hydration is expressed in terms of C, the number of water
molecules per nucleotide.
Sevilla et al. have shown that HO
.
is not detected in relatively dry DNA (C < 8), but
is detected in the C > 8 waters per nucleotide, suggesting that all holes do not transfer to
DNA in the regime (8 > C > 22). The sites where these holes are initially produced are
not particularly good hole traps. The holes move about until they encounter deep traps
such as guanine.
The aqueous electron will react rapidly with all four of the nucleobases. Reaction of
the aqueous electron with deoxyribose or ribose phosphate is 2 orders of magnitude lower,
so the dominant interaction is with the bases.
2.5. Focus of this Chapter is on Direct-Type Damage
Von Sonntag [7] has estimated that the direct eects contribute about 40%to cellular DNA
damage, while the eects of water radicals amount toabout 60%. Apaper byKrischet al. [15]
on the production of strand breaks in DNA initiated by HO
.
radical attack has the direct
eects contribution at 50%.
Indirect-type damage is much better characterized, both quantitatively and mecha-
nistically, than its direct-type counterpart. Since indirect-type damage has been thoroughly
reviewed by von Sonntag [7] and by ONeill [16], the emphasis of the present chapter will
be direct-type damage.
3. DISTRIBUTION OF INITIAL DIRECT-TYPE DAMAGE IN DNA
3.1. Predictions Based on Physics of Ionization and Electron Trapping
Ionizing radiation produces nonspecic ionizations; it ionizes DNA components approx-
imately in direct proportion to the number of electrons. The sugar-phosphate backbone
contains 52% of the electrons; the average base contains 48%. Electron paramagnetic
resonance (EPR) experiments have shown, however, that the nal damage to DNA is not a
random distribution among these three components. Rather, the majority of the radicals
are on the DNA bases. Furthermore, the radiation damage is not randomly distributed
among the bases. At low temperatures (410 K), one nds initial trapping of the excess
electron primarily by cytosine and secondarily by thymine and, upon warming to 180k,
primarily by thymine. The radical cations are localized almost exclusively on guanine
(which has the lowest gas-phase ionization potential).
The low-temperature EPR experiments used to determine the DNA ion radical
distribution make it very clear that electron and hole transfer occurs after the initial
random ionization. What then determines the nal trapping sites of the initial ionization
events? To determine the nal trapping sites, one must determine the protonation states of
the radicals. This cannot be done in an ordinary EPR experiment since the small hyperne
couplings of the radicals only contribute to the EPR linewidth. However, detailed low-
temperature EPR/ENDOR (electron nuclear double resonance) experiments can be used
to determine the protonation states of the low-temperature products [17]. These proto-
nation/deprotonation reactions are readily observed in irradiated single crystals of the
DNA base constituents. The results of these experiments are that the positively charged
radical cations tend to deprotonate and the negatively charged radical anions tend to
protonate.
To predict which of the initial ionization events will recombine, and which ones
will lead to a stably trapped radical, one must consider the molecular environment. For
example, after irradiation, 1-methylcytosine (1-meCyt) is known to have a very low free
radical yield, so it is argued that a large percentage of the initial radicals formed by the
ionizing radiation must recombine. The hydrogen-bonding network of 1-meCyt does not
favor long-range proton displacements [18]. Consequently, there are no energetically
favorable paths which would promote the separation of unpaired spin and charge, leaving
the initial sites prone to recombination. On the other hand, in many of the systems
considered here, there are ecient pathways for returning ionization sites to their original
charge states, thereby eectively inhibiting recombination. As a consequence, many of the
radiation-induced defects reported are not the primary radiation-induced events, i.e.,
radical cations or anions, but rather neutral products (deprotonated cations or protonated
anions), which are less susceptible to recombination.
These ideas have been illustrated in a recent study of the co-crystalline complex of 1-
meCyt:5-FUra [19]. Using model calculations, it was shown how the hydrogen-bonding
network of the crystal is able to sustain a proton shuttle which leads to the selective forma-
tion of certain radicals. Calculations predict that the site of reduction would be the cytosine
base, yielding the N3 protonated cytosine anion, Cyt(N3+H)
.
, while the uracil base
would be the site of oxidation, yielding the N1 deprotonated uracil cation, Ura(N1H)
.
(see Fig. 1 for radical structures and notation). These are indeed the primary radiation-
induced species observed experimentally [19].
There seems, however, to be a problemwith the above reasoning. If all the free radical
damage ends up on the DNA bases, then one has problems explaining signicant lesions
such as single-strand breaks. How then does one explain strand breaks? The question could
be rephrased by asking if there could be damage to the ribose-phosphate which is dicult to
detect.
A single ionization event creates a hole and an ejected electron. To maintain charge
neutrality, if a hole is trapped, then an electron is also trapped. Therefore the radical yield
must consist of equal oxidation (e
removal) and reduction (e
trapping) events. The

electron addition half occurs exclusively at the bases, while the electron loss half occurs
according to the number of electrons per component. That means 52% of the holes are
initially generated on the sugar phosphate, corresponding to 26% of the initial radicals. A
Figure 1 Free radical structures, parent compounds, and stable end products for the various
components of DNA: (a) deoxyribose, (b) guanine, (c) adenine, (d) thymine, and (e) cytosine. Panel
(f) shows trapping of the electron and hole by proton transfer in the GC base pair in duplex DNA.
recent paper has demonstrated that small percentages of the common H-abstraction sugar
radicals could be present in irradiated DNA but could not be detectable in powder samples
[20].
3.2. Initial Trapping Sites of Holes and Excess Electrons Observed by
Low-Temperature EPR/ENDOR
Model Systems
Before discussing the types of radicals actually observed in DNA, it is important to rst
summarize the work on model systems. These include studies of irradiated nucleosides and
nucleotides from which one can usually determine the structures of the free radical
products. The emphasis here will be to summarize the results on EPR/ENDOR studies
of irradiated DNA bases at low temperatures in eorts to study the primary radiation-
induced defects.
Figure 1 Continued.
Figure 1 Continued.
Reduction of cytosine produces a radical with sites of unpaired spin density at
C2, C4, and C6. The hyperne coupling of the unpaired spin with the C6H
a
produces a
1.4-mT doublet, which is the main EPR feature of one-electron reduced cytosine
observed in various cytosine derivatives [21].
The cytosine anion, Cyt.
.
, is a strong base (pK

a
>13) [22] and is therefore expected
to rapidly protonate in solution. Hissung and von Sonntag [23] have shown by con-
ductance techniques that the radical anion of cytosine is protonated by water (most likely
at N3 or O2) in less than 4 nsec. From studies of cytosine monohydrate single crystals
irradiated at 10 K, Sagstuen et al. [24] concluded that the primary reduction product is the
N3 protonated anion, Cyt(N3+H)
.
. ENDOR experiments detected the C6H
a
hyperne
coupling, the N3H
a
hyperne coupling, and one of the small couplings to the N4H
2
protons.
Oxidation of cytosine produces a radical with sites of unpaired spin density at N1, N3,
and C5. The cytosine cation has a pK
a
<4 and in solution deprotonates at NH
2
[22]. In the
solid state, Sagstuen et al. [24] assigned the primary oxidation radical observed in cytosine
monohydrate as the N1 deprotonated cation, Cyt(N1H)
.
. It is known from the ENDOR
Figure 1 Continued.
experiment that the unpaired electron densities, U, are U(N1)=0.30 and U(C5)=0.57.
Furthermore, there are two small exchangeable NH couplings whose angular variations
correlate well with the exocyclic N4H
2
protons.
Since an oxidation product on cytosine in DNA could not deprotonate at N1, it may
be more relevant to look at oxidation in a nucleotide. In 5V-dCMP (where N3 is protonated
in the parent molecule), oxidation produces the N3 deprotonated cation, Cyt(N3+H
+
,
N3H)
.
, with U(N1)=0.30 and U(C5)=0.60 [25].
Some time ago, an allyl-like radical was observed in irradiated crystals of 5V-dCMP
[26]. This radical was thought to be a sugar radical, although no likely scheme was
proposed for its formation. It now appears that this radical is formed on 5-methyl cytosine
impurities in these crystals [27]. This radical forms by deprotonation at the methyl group
of the cytosine cation, 5meCyt(MeH)
.
, and may have important consequences in the
radiation chemistry of DNA since the ionization potential of 5-methyl cytosine is lower
than that of either cytosine or thymine.
The thymine anion radical has been identied in duplex DNA when it is exposed to
ionizing radiation at temperatures of 77 K or below [28]. Evidence for this radical assign-
ment comes from measurements that demonstrate the conversion of an EPR doublet
associated with the thymine anion into a readily identiable eight-line spectrum of the 5,6-
dihydrothymine-5-yl radical [29,30]. This conversion is due to the protonation of the thy-
mine anion at C6. While this process seems rather straightforward, questions remain about
the fraction of the free radical population assignable to the thymine anion (reduction will
Figure 1 Continued.
also occur at cytosine) and whether or not the thymine anion protonates at C4jO prior to
protonation at C6.
The thymine anion is only a weak base (pK
a
=6.9) [22]. This means that protonation
of the anion may depend on the specic environment. The primary reduction product
observed in the solid state in thymine derivatives is the C4OH protonated anion [17]. This
species exhibits signicant spin density at C6 and O4. Here one must distinguish between
two dierent situations. In single crystals of thymidine, the C4OH
h
proton is out of the
molecular plane which gives rise to an additional 33.1-MHz isotropic hyperne coupling
[31]. A similar situation is observed in single crystals of anhydrous thymine [32]. In 1-
meThy, however, the C4OH
h
proton is in the molecular plane. Consequently, the proton
coupling is very small.
There is not much discussion of thymine oxidation products since they are viewed as
unimportant in the radiation chemistry of DNA, the feeling being that in DNA, most of
the holes will be trapped by the purines. However, when model systems are used, there are
several known pathways that involve oxidation of the thymine base. When a thymine base
is ionized, the resulting thymine cation is an acid with pK
a
=3.6 for deprotonation in
aqueous solution [22]. The thymine cation will likely deprotonate at N3, Thy(N3H)
.
,
although one must look for alternative routes for the cation to eliminate excess charge
if N3 is not hydrogen-bonded to a good proton acceptor. One could have reversible
deprotonation of the thymine cation at N3 or irreversible deprotonation at the C5CH
3
.
In all thymine derivatives studied so far in the solid state, there is always a signicant
concentration of a radical formed by net H abstraction from the >C5CH
3
group,
Thy(MeH)
.
[17]. This allyl-like radical is present at helium temperatures. From studies of
frozen thymine solutions and poly(T), it can be shown that the precursor of the allyl-like
radical is the thymine cation [33,34].
There has been continued interest in the radiation chemistry of the purines since
early reports on oriented DNA by Gra slund et al. [35] which suggest that the main
trapping site of one-electron oxidation in DNA is the guanine base. It is remarkable that in
aqueous solution, the electron adducts of the purine nucleosides and nucleotides undergo
irreversible protonation at carbon with a rate constant 2 orders of magnitude higher than
that for carbon protonation of the electron adduct in thymidine [36]. It is therefore
important to know the properties of the various purine reduction products and to ask why
they have not been observed in irradiated DNA.
In single crystals of 5V -dGMP, the native molecule is not protonated at N7. EPR/
ENDOR experiments detected a narrow doublet whose hyperne coupling correlates with
a C8H
a
interaction. The computed spin density was U(C8)=0.11. This radical was un-
stable on warming above 10 K, and therefore it was proposed that the radical responsible
was the pristine radical anion [37]. However, it is possible that the guanine C6OH
protonated anion could explain these data. One-electron reduced guanine deprotonates
at 10 K, but then the protonation reverses upon warming, leaving the original anion, which
is then subject to recombination.
The guanine radical cation is a weak acid (pK
a
=3.9) [22]. Therefore deprotonation will
depend on the environment. Bachler and Hildenbrand [38] have studied the guanine
oxidation product in aqueous solution of 5V -dGMP. The best t to their EPR spectra seems
to be from the radical cation (Gua
.
+
).
In the solid state, oxidation of 5V -dGMP at 10 Kleads to deprotonation at the exocyclic
nitrogen, Gua(N2H)
.
, which is characterized by U(C8)=0.175 and U(N2)=0.33 [37]. The
same radical was detected in crystals of 3V ,5V -cyclic guanosine 5V -monohydrate. In this second
study, the N3 spin density was determined to be 0.31 [39].
Some experiments have been performed on guanine molecules that were originally
protonated at N7. Subsequent electron loss by this molecule leads to deprotonation at
N7 yielding Gua(N7+H
+
, N7H)
.
, which is equivalent to the guanine radical cation.
The experimental results from this guanine cation have U(C8)=0.18, U(N2)=0.17, and
U(N3)=0.28 [40].
It is not clear what the structure of one-electron oxidized guanine is in DNA. The
amino-deprotonated product observed in 5-dGMP does not seem to t parameters of the
oxidation species observed in DNA. Recently, Reynisson and Steenken have proposed
that the one-electron oxidized species found in ds DNA is the radical cation [41].
The adenine anion has a pK
a
=3.5 [22]. After electron capture, the negative charge of
the adenine radical anion resides mainly on N1, N3, and N7 and therefore protonation likely
occurs at one of these nitrogens. The results show that in single crystals examined at 10 K,
that reduction of adenine leads to the N3 protonated adenine radical anion, Ade(N3+H)
.
,
with spin densities of ca. U(C2)=0.41, U(C8)=0.14, and U(N3)=0.12 [42].
The adenine radical cation was observed in a single crystal of adenine hydrochloride
hemihydrate [43]. In this crystal, the adenine is protonated at N1. After electron loss, the
molecule deprotonates at N1, giving Ade(N1+H, N1H)
.
+
. This produces a radical that
is structurally equivalent to the cation of the neutral adenine molecule with spin density on
C8 and N6 [U(C8)=0.17 and U(N6)=0.25]. The adenine radical cation is strongly acidic
(pK
a
<1) [22]. This strong driving force makes the reaction independent of environmental
conditions. In single crystals of adenosine [42] and anhydrous deoxyadenosine [44], the N6
deprotonated cation [Ade(N6H)
.
] is observed which is characterized by U(C8)=0.16 and
U(N6)=0.42. The experimental isotropic hyperne couplings are N6H
a
=33.9 MHz and
C8H
a
=12.4 MHz.
In single crystals of deoxyadenosine [45], the site of oxidation seems to be the
deoxyribose moiety. This brings up an interesting point. In studies of the radiation-
induced defects in nucleosides and nucleotides, one often sees evidence of damage to the
ribose or deoxyribose moiety. These radicals have not been discussed here because much
less is known about sugar-centered radicals in irradiated DNA.
DNA
The previous section outlined the typical e
loss and e
gain products observed in the nucleic

acid bases in the solid state. These studies can be applied to the study of the radiation
chemistry of DNA. The relevance of the study of model systems is shown by considering the
following remarkable observations. Years ago, Ehrenberg et al. showed the EPR spectra of
the 5,6-dihydrothymine-5-yl radical observed in thymine, thymidine, and DNA. The spectra
are nearly identical [46]. The reduction product observed in cytosine monohydrate is the N3
protonated anion. In solution, this reduction product gives rise to a 1.4-mT EPR doublet.
The same feature is present in irradiated DNA at 77 K. Likewise, the result of e
loss in
guanine bases is characterized by a broad EPRsinglet. The same feature is also evident in the
EPR spectrum of DNA irradiated and observed at 77 K.
The EPR spectrum of irradiated DNA is not very well resolved. Attempts to improve
the spectral resolution have used deuterated DNA and samples of oriented DNA. Using
oriented DNA, Gra slund et al. [35] suggested the thymine anion Thy
and the cytosine

cation Cyt
.
+
were also considered possibilities. Later work reported that only Gua
.
+
and
Thy
.
were present [47].

Another method is to produce EPR basis spectra by irradiating various nucleic acid
bases. The EPR spectrum of DNA is simulated by taking various combinations of the
basis spectra. For example, Bernhard looked at one-electron reduction of d(pApGpCpT)
at 4 K. The spectrum of the reduced tetramer was simulated by using basis spectra of Thy,
Cyt, Ade, and Gua radical anions [48]. The conclusions were that 80% of the trapped
electrons resided on cytosine and the remaining 20% on thymine. It should be pointed out
that it is dicult to know these percentages precisely since the EPR spectra of reduced Thy
and Cyt are quite similar. (At X-band microwave frequencies, this is more so than at Q-
band.) Therefore small changes in the Thy/Cyt ratio do not aect the outcomes of the
simulations very much.
Sevilla et al. [49] have simulated the EPR spectrum of whole DNA equilibrated with
D
2
O irradiated and observed at 77 K. The results were 77% Cyt
.
and 23% Thy

.
for the
anions and >90% Gua
.
+
for the cations. The analysis produced a small imbalance in
the cations (44%) and anions (56%). It was suggested that some holes remain trapped in
the solvation shell. It is also possible that this reects small errors in the treatment of the
basis spectra, or that some DNA radicals are not accounted for because their EPR signal is
too broad and poorly resolved.
Another approach by Hu ttermann et al. [50] has been to use pulsed EPR techniques
to study the radicals present in DNA bers equilibrated in D
2
O and then irradiated and
observed at 77 K. This work supports the conclusions that the primary radiation-induced
defects are Cyt
.
and Gua
.
+
. Also reported are contributions from Thy
.
and an allyl
radical found on thymine [Thy(MeH)
.
]. Also discussed are three components tentatively
assigned as adenine and guanine anions and a species whose dominant hyperne
interaction involves the N1 of cytosine.
More recently, this same group has studied DNA with high-eld EPR (245 GHz)
[51]. This study shows nice spectra of the Thy(MeH)
.
radical. Also, the authors discuss
the eects of hydration levels on the production of the various base radicals. A more
recent paper by Weiland and Hu ttermann [52] considers the same base radicals in DNA at
77 K and then looks at the transformation of these radicals into the more stable room-
temperature products. Among these are C1V and C3V sugar radicals, dRib(C1VH)
.
, and
dRib(C3VH)
.
, respectively.
3.3. Predictions Based on Computational Chemistry
Several recent papers have reported Density Functional Theory (DFT) calculations on the
primary oxidation and reduction products observed in irradiated single crystals of the
common nucleobases: thymine [53], cytosine [54], guanine [55], and adenine [56]. The theo-
retical calculations include estimates of spin densities and isotropic and anisotropic
hyperne couplings which can be compared with experimental results (obtained from
detailed EPR/ENDOR experiments).
It should also be pointed out that the calculation of accurate hyperne coupling
constants is rather dicult. Two factors are involved: the isotropic component (A
iso
) and
the anisotropic component (T
xx
, T
yy
, T
zz
). One must have a good description of electron
correlation and a well-dened basis set in order to calculate accurate isotropic hyperne
couplings. This is not easy to do with molecules the size of the DNA bases. Even when the
computational demands are met, the theoretical calculations may deviate more than 20%
from the experimental results. Recently, it has been shown that the calculation of aniso-
tropic hyperne couplings for hydrogens is often within 510% of the experimental values
[54]. The goal is to make comparisons of calculated and experimental isotropic and
anisotropic hyperne couplings a useful guide in identifying radiation-induced free
radicals.
The present level of theoretical work can be seen in a recent paper by Sevillas group.
They have employed DFT to study the details of proton transfer reactions in Gua:Cyt
base pairs [57]. Using the DFT functional B3LYP with the 631+G(d) basis set on the
entire Gua:Cyt molecule (19 heavy atoms), the results are presented which show that it is
energetically favorable for the N1 proton of guanine to transfer to the N3 of cytosine after
reduction of cytosine or after oxidation of guanine.
Several additional problems must also be considered. The calculations discussed here
are computationally challenging. They involve a single-point calculation on the optimized
structure using triple-zeta plus polarization functions [B3LYP/6311G(2df,p)] in order to
compute spin densities. Also, the detailed DFT calculations were performed on isolated
molecules, whereas some of the experimental results reported involve free radical formation
in the solid state, mainly in single crystals. Therefore the theoretical calculations are ignoring
the electrostatic environment of the radicals discussed, in particular, the intricate hydrogen-
bonding structure that the free radicals are imbedded in. This often leads to nonplanar
radicals which may or may not represent what is believed to be observed experimentally in
the solid state.
In many cases, the theoretical and experimental results agree rather well. In other
cases, there are discrepancies between the theoretical and experimental results. A review of
the successes and failures of using DFT to calculate spin densities and hyperne couplings
of the primary radiation-induced free radicals observed in the nucleobases has recently
appeared [58].
3.4. DNA Stopping Power
Invaluable to understanding the spatial distribution of damage in DNAare calculations that
employ Monte-Carlo track-structure simulations [5962]. Since most of the energy loss is
through inelastic interactions between fast electrons and the DNA, the cross sections for
energy loss by electrons are of critical importance. While most theoretical calculations are
based on the stopping power of gaseous water, it has been pointed out by La Verne and
Pimblott [63,64] that the most probable energy loss and the mean energy loss for electrons in
DNAdo not compare favorably with gaseous water but are reasonably close to liquid water.
Their calculation was based on inelastic cross sections that are obtained from the dipole
oscillator strength distribution of DNA. They calculate a mean energy loss for a 1-MeV
electron in DNA of 57.9 eV, close to the value of 56.8 eV for liquid water but diering
substantially from 50.9 eV for gaseous water. In order to compare experimentally deter-
mined yields and degree of clustering with the calculated track structures, it would help
considerably to have more concrete information on the stopping power of DNA.
One important application of track-structure calculations is in understanding exper-
imental measurements of free radical yields in DNA, particularly crystalline DNA. Cur-
rently, the yield of initial ionizations in DNAis unknown. As a proxy, one can use the values
for water (low LET): G(initial ion)
f
G(OH)+G(eaq)+G(H)=0.59+0.50+0.09=1.18
Amol/J [65]. If the stopping power of DNA is the same as liquid water, then samples such
as crystalline DNA should yield 1.18 Amol/J initial ionizations at low LET. At 4 K, the ob-
served yields of 0.550.78 Amol/J [66,67] would require that 5070%of the initial ionizations
are stably trapped. To the degree that the DNAstopping power might be greater than that of
water, this percentage goes downandthe range of electronor hole transfer must be increased.
If the data on cross sections of low-energy electrons with DNA [68] could be integrated into
the Monte-Carlo track-structure calculations, it should help close this gap between experi-
ment and theory.
4. TRACK EXPANSION AND CHARGE MOBILITY IN DNA
4.1. Track Expansion Affects the Spatial Distribution of Products
The nonhomogeneous distribution of energy absorption is a dening characteristic of
ionizing radiation. If this characteristic had been absent, the unique impact of ionizing
radiation in biology and medicine would almost certainly not exist. But the fact that
energy deposition is spatially nonhomogeneous is not, in itself, sucient to explain the
high toxicity of ionizing radiation. The high toxicity (lethality, mutagenicity, and
carcinogenicity) is a consequence of the fact that the nal damage produced in DNA is
spatially nonhomogeneous. The severity of the biological consequences depends on the
degree to which stable products are formed in clusters [69] or, in dierent words, occur as
multiply damaged sites [70]. An inevitable conclusion is therefore that the rate of product
formation must be competitive with the rate of track expansion. Clustered products evolve
from clustered ionizations.
Fig. 2 depicts, in schematic, the two extremes plus an intermediate case of track
expansion. InFig. 2A, the initial distributiononions is shown at zerotime, where t=0 is after
thermalizationbut before charge transfer. The initial cluster density is a functionof LET, and
even at very lowLET (e.g.,
60
Co g-rays), a large percentage of energy is deposited in clusters
[71]. In Fig. 2B, ion mobility is high, which would be the case if DNAwere a good conductor.
After a very short time, combination reactions fully annihilate the charges in DNA. In Fig.
2C, the holes and excess electrons have low mobility, moving a short distance before
trapping. Closely spaced, opposite charges combine. In Fig. 2D, the mobility is zero; the
track is etched in place. We consider case B rst, the case where holes and electrons freely
conduct through the base stacks, consequently leaving no damage on the base stack.
Figure 2 A schematic representation of track expansion is shown assuming dierent mobilities. (A)
Spatial distribution of radical ions at the sites of initial thermalization. (B) When there is high
mobility, that of a conductor is assumed, no radical ions are trapped on DNA. (C) If there is low
mobility, some radical ions are trapped while others recombine. (D) At zero mobility, the spatial
distribution of trapped radicals is the same as in the initial track, i.e., the same as in (A).
If DNA has the properties of a molecular wire, as proposed in 1993 [72] and sub-
sequent work (e.g., Refs. 7376), then the spatial distribution in DNAwould look something
like that in Fig. 2B. If this was the case, it is very dicult to reconcile a large body of
knowledge in radiation biology because not only does it dramatically reduce the degree of
clustering, it would also make DNA remarkably radiation-resistant. Indeed, base damage
produced via the direct eect would not exist. Publications by radiation chemists and theo-
reticians, before and after the 1993 proposal, provide rather strong evidence that DNAis not
a molecular wire [7779]. Joining that body of work is a recent series of photochemistry
investigations that shows that charge mobility through DNAis that expected of an insulator
(a poor semiconductor) [8082]. Therefore the situation under Fig. 2B does not occur.
The other extreme shown in Fig. 2D also does not occur. Holes are mobile. We know
this because, as discussed above, the probability of nding a hole on a particular component
does not correlate with the probability of ionization. Holes are trapped preferentially at
guanine [83], to a lesser extent at the sugar [84], and rarely at the other bases. This
redistribution requires hole transfer. Trapping of the excess electron is also selective,
occurring primarily at cytosine [49,85,86]. This implies that after thermalization, the electron
transfers between bases until nding a stable trapping site. Therefore the situation is as
depicted in Fig. 2C. Akey question is What is the range of both the excess electron and the
hole within DNA and through its local environment?
4.2. Hole and Electron Transfer
Studies of the direct eect have been largely conned to DNA samples in the solid state.
This is done in order to maximize direct-type damage and minimize indirect-type damage.
In addition, low temperatures are often employed both as a means of sequestering the
DNA from the bulk water and as a means of stabilizing free radical intermediates. In
frozen DNA samples, the mobility of holes and excess electrons diers for the dierent
sample components: ice, solvation shell, DNA backbone, and base stacks. We start with
the ice phase.
Ice
In an aqueous solution of DNA, the water outside of the solvation shell is referred to as bulk
water. When DNAsolutions are frozen, the bulk water crystallizes as a separate phaseice.
Ice does not formif the concentration of DNAis brought to a level where only the solvation
shell remains, about 2022 waters/nucleotide. If brought to this concentration slowly, a lm
is formed. Freezing a lm does not create ice. Another type of sample is prepared by rst
lyophilizing DNAand then letting it sit at a preselected humidity that determines the level of
hydration, typically 2.5<G<22. Subsequent freezing of these cotton-like samples does not
yield ice.
During irradiation, the holes produced in the ice phase are sequestered by the ice. This
is not strictly true for the excess electrons; some escape the ice phase and are selectively
scavenged by DNA. The degree to which this increases the yield of electrons trapped by
DNA is considered to be relatively small and therefore when computing yields of direct
damage in DNA, the mass of the ice phase is usually excluded fromthe target mass. While ice
is a relatively passive component of the system, it does provide an important reference point
with respect to product yields. Electrons and holes are quite mobile in ice [87,88]; it is a
decent conductor. Consequently, even at low temperatures, the free radical yields are quite
low, e.g., the yield of HO
.
in ice at 77 K is 0.037 Amol/J [83]. This is just one example of a
general principle; high charge mobility promotes recombination and therefore results in low
yields of trapped free radicals.
DNA Solvation Shell
Ionization of DNAs solvation shell produces water radical cations (H
2
O
.
+
) and fast
electrons. The fate of the hole is dictated by two competing reactions: hole transfer to
DNA and formation of HO
.
via proton transfer. If the ionized water is in direct contact
with the DNA (G<10), hole transfer dominates. If the ionized water is in the next layer
out (9<G<22), HO
.
formation dominates [67,89,90]. The thermalized excess electrons
attach preferentially to bases, regardless of their origin. Thus the yield of one-electron
reduced bases per DNA mass increases in lockstep with increasing G, up to an G of 20
25. This means that when G exceeds 9, there will be an imbalance between holes and
electrons trapped on DNA, the balance of the holes being trapped as HO
.
. At G = 17, an
example where the water and DNA masses are about equal, the solvation shell doubles
the number of electron adducts, increasing the DNA-centered holes by a bit over 50%
[9193].
Samples that are prepared by freezing DNAsolutions result in a DNAaggregate phase
in which ice formation draws water from the solvation shell. The net result is that the DNA
aggregates have an average G of
f
15 [89,90]. For DNA prepared in this manner, the target
mass is DNA+15 waters [91]. Since the solvation shell is not pure water, containing about
one cation per nucleotide, it is more accurate if one replaces water mass by the equivalent
cation mass. Taking Na
+
as an example, 15 waters would be replaced by the sum of 1
Na+13.5 waters. A rule of thumb is that if one assumes that only the DNA is the target
mass, the solvation layer of DNA doubles the direct-type damage.
DNA Backbone
Forward reactions of the one-electron oxidized sugar-phosphate backbone are of two types:
hole transfer to the base stack or formation of a neutral sugar radical by irreversible
deprotonation. In much of the older literature, it was assumed that the former eclipsed the
latter. This was largely because free radicals centered on the sugar moiety were not detected
by EPR. As has been pointed out, this does not prove that sugar radicals are not formed
[94,95], and indeed, computed simulations have shown that such radicals would give EPR
spectra that would be dicult to detect in the presence of the intense signal from the base-
centered radicals [20,96]. Recent results leave little doubt that a substantial fraction (
f
25%)
of the holes are irreversibly trapped on the sugar [84,9799].
Evidence that direct-type damage occurs at the sugar consists of the following. Becker
et al. [100] observed sugar radicals in DNA exposed to high LET radiation. Swarts et al.
[101] observed free base release in DNA and Razskazovskiy et al. [98] observed free base
release in crystalline oligodeoxynucleotides. Free base release correlates with sugar damage.
The yields of strand-break products have been measured by Debije et al. [97] and
Razskazovskiy et al. [99] in crystalline oligomers x-irradiated at 4 K. Debije has identied
a 3V -centered sugar radical in crystals of d(CTCTCGAGAG)
2
, a B-form DNA [84]. Broadly
speaking, 1020% of the radicals initially stabilized on DNA at 4 K are sugar radicals. This
corresponds to about half of the backbone-centered holes (formed directly and indirectly by
transfer from water) leading to neutral sugar radicals via deprotonation of the one-electron
oxidized sugar-phosphate backbone. Also, it correlates well with the observed yields for
direct strand breaks, 0.050.15 Amol/J, in high molecular weight DNA (Sec. 5).
DNA Bases
Radiation Chemistry. It has been known for decades that charge migrates through
the stacked bases of DNA [102,103]. Compelling evidence comes from studies employing
EPR [30,77,104106], pulse radiolysis [107,108], and product analysis [101,109,110]. The
range of migration for electron and holes at 477 Kis at least 2 bp and the mean is between 3
and 11 bp [106,111]. Warming samples above 150 K extends thermally activated migration
to 30 bp or more [106]. Clearly, the DNA bases are very eective traps for both holes and
excess electrons. Because the activation energy needed to detrap these species is very disperse
[104], charge migration by hopping can be observed over a wide temperature rage,<20 to
>150 K. The dielectric relaxation that creates traps most assuredly occurs even at room
temperature, competing with other processes such as tunneling. While it may be dicult to
observe these trapping events at room temperature, one should anticipate that they
moderate the speed and range of charge transport, even at high temperatures and in
dilute aqueous solution.
Photochemistry. The proposal by Murphy et al. [72] that DNA is a molecular wire
stimulated newinterest in the possibility that DNAconducts charge through its base stacks,
particularly among photochemists. Based on an observed absence of uorescence, they
concluded that electron transfer occurs through a length of stacked bases (k-ways) >4.0
nm in<10
9
sec. They calculated h
e
f
0.2 A
1
for the equation k
ET
=k
0
exp{h
e
(RR
0
)},
where, for the case of tunneling, the electron transfer rate is expected to drop o
exponentially as a function of distance (RR
0
). Conductors do have very low values of
h
e
, such as Murphy et al.s group observed. The high conductivity of DNA was eventually
promoted as a paradigm shift [112,113]. Others, using the tools of photochemistry, have
measured the values of h, making sure of high quantum yields and conrming transfer with
corroborating evidence. For electron transfer and for hole transfer, h
e
f
1.0 A
1
and
h
h
f
0.6 A
1
are obtained, respectively, values typical of insulators [114116]. If
experiments are designed that are permissive for hopping, then low values of h
h
,<0.2
A
1
, can be observed, but under these circumstances, electron transfer is not fast [117]. In
our opinion, the evidence is conclusive; DNA is an insulator. The current questions of
interest focus on how excess electrons and holes move through DNA and what reactions
compete with charge transfer. Indeed, electron transfer in DNA proceeds independently of
the k-ways, the main function of which is to promote base stacking and thereby stabilize
the linearity of DNA.
Interstrand and Interduplex
DNADNA. While it is dicult to design an experiment that proves that electron/
hole transfer occurs between the strands of a single duplex (interstrand), it is rather simple to
prove that transfer occurs from one duplex to another (interduplex). This was done by
monitoring the concentration of holes and excess electrons trapped in crystalline DNA as a
function of temperature. Given that the annealing characteristics are relatively insensitive to
DNA conformation, sequence, or base stacking continuity, it is readily shown that electron
and/or hole transfer must be intermolecular [104]. In more elegant experiments (see below),
it is shown that interduplex tunneling occurs for both electrons and holes [118121]. These
newresults make it clear that, with regard to charge transfer via tunneling, the key variable is
distance, not the intervening covalent or k-bonds. Thus in a crystalline lattice, where the
tunneling distance between helices is comparable to that within a strand, the hole and
electron move in three dimensions.
If hole and electron transfer occurs interduplex, it follows that it will also occur
interstrand. The tunneling distances are comparable. This is elaborated in Sec. 4.3.
DNAProtein. A large number of proteins in nature perform their function by
expediting electron transfer, and there is an extensive literature on electron transfer through
proteins (see Refs.122124 for reviews). Relevant here are the observations that the excess
electron has a large range (not readily trapped) [125] while the hole is relatively immobile
(trapped by deprotonation at the peptide bond giving amido radicals) [126]. This raises the
expectation that electrons but not holes could be transferred fromprotein to DNA. This has
been observed by a number of groups [127131].
In one of the more detailed studies to date, Weiland and Hu ttermann [131] compare
the trapped radical distribution of DNA alone with that of dry chromatin. Using high-eld
EPR (285 GHz), these experiments signicantly reduce the spectral overlap between one-
electron oxidized guanine (Gua
ox
) and the other DNA radicals thereby improving the
precision over EPR measurements made at lower elds (9 GHz). Following x-irradiation at
77 K, the DNA samples trap out 55% of the radicals as one-electron reduced pyrimidines
(Pry
re
) and 22% as one-electron oxidized guanine. Under the same conditions, chromatin
gives 26% and 5%, respectively. The radical concentration at a specic dose increases by
1.4 in chromatin vs. DNA alone. Given that
f
47% of the radicals are preferentially on
DNA and that the chromatin samples consisted of
f
30% DNA and
f
70% histone
proteins, the authors nd that the concentration of radicals trapped by DNA in chromatin
is
f
2 that of DNA alone. The data can be used to estimate the inux of electrons (x) and
presumed eux of holes ( y). Solving the two equations, 100 +x y =200 and 26/5 =(55
+x)/(22 y), one obtains x =94 and y =6. Thus these results indicate that when DNAis
packaged in chromatin (dry), it traps twice as many electrons while hole trapping is relatively
unchanged. Warming the 77 K irradiated chromatin to 300 K reduces the total radical
concentration by at least 95% while not causing any marked changes in the DNAprotein
radical ratio. This means that electrons or holes are thermally mobilized in both compo-
nents, but there is no net exchange between the components.
The amount of information is still insucient to predict how packaging of DNA in
chromatin modies the nal product distribution in DNA. If the stable end products
reect a doubling in reductive damage while oxidative damage remains the same, then one
would expect an increase in frequency and complexity of clustered lesions. If that proves
true, the histone proteins and attending nucleosomes structure would act as radiation
sensitizers.
4.3. Tunneling and Hopping
Charge transfer in DNA occurs under two distinctly dierent conditions: one which is
temperature-independent and the other which is not. The mechanism underpinning the
former is tunneling, while the latter is controlled by an activation barrier that must be
hopped over. Of these two, tunneling is the one better characterized.
Tunneling
Tunneling as a mechanism of charge transfer in DNA has received widespread attention
(see, for example, Refs. 117 and 132). Recently, denitive proof that tunneling in DNA
occurs has been reported by Sevilla et al. [118121,133]. Key to this proof is the demon-
stration that the observed rates of hole and electron transfer are independent of temperature
from 4 to 130 K. We summarize their ndings here.
DNA, laced with an intercalator characterized by a high electron anity, is g-ir-
radiated and observed by EPR. The one-electron reduced intercalator presents an EPR
spectrum that is readily distinguishable from that of the DNA-trapped radicals. A key
example is mitoxantrone (MX), with an electron anity of 6.25 eV and a radical anion
spectrum that is a sharp singlet. Charges are injected into the DNA by g-irradiation at a
preselected temperature (4130 K). Holding the temperature constant, the EPR spectrum
changes as a function of time (0.530 h). Thereby, a direct measure of the rate of electron
transfer from one-electron reduced pyrimidines (Pry
re
) to the intercalator, e.g., MX,
is measured. The tunneling rate is observed to depend on the electron anity (EA) of the
acceptor (intercalator): for MX, h
e
= 0.9F0.1 A
1
and k
0
f
10
11
sec
1
, and for ethidium
bromide (EA=4.32 eV), h
e
=1.2 F0.1 A
1
and k
0
f
10
5
sec
1
. It also depends on the EAof
the donor (Pry
re
). The calculated EA of the Ade:Thy and Gua:Cyt base pairs are 0.30 and
0.49 eV, respectively [57,134]. The values of h
e
are 0.7F0.1 and 1.4F0.1 A
1
for Thy
re
and Cyt
re
, respectively. In addition, the rate depends on DNADNA distance, proving that
tunneling is intermolecular as well as intramolecular. In addition, the values of h are not
strongly dependent on the medium lying between the donor and acceptor. If intermolecular
transfer is not takenintoaccount, calculationof the transfer distance gives a deceptively large
number, e.g., 31 base pairs reported by Pezeshk et al. [135]. Taking intermolecular transfer
into account, the tunneling distance at long times (1 hr) is remarkably reproducible for MX-
DNA over a wide range of DNA packing congurations, 3538 A
(1011 base pairs). For

hole transfer in MX-DNA, h
h
equals 1.1 A
1
assuming a value of k
0
of 110
11
sec
1
.
Two important insights into the spatial separation of end products grow out of the
recent ndings on tunneling in DNA. (1) In order for the distance between the stable
products derived from oxidized guanine and reduced pyrimidines to be less than 3040 A
(<10 bp), a competing irreversible reaction must trap the radical at a rate competitive with
that of tunneling. While this is highly improbable at low temperatures,<120 K, it is likely
to be signicant at RT. More needs to be learned about the rates of irreversible trapping.
(2) The rate of irreversible trapping of holes on the sugar must be fast relative to hole
tunneling to the bases. This means that the distance between a strand break (derived from
the sugar-centered hole) and base damage may be substantially less that 30 A
. The neutral
sugar radical will not be a strong getter for base radicals. One predicts therefore that a
clustering of strand breaks with base damages will be more prevalent than clustering of
base damage with base damage when DNA is irradiated at low temperatures. How this
shifts, when irradiation is at RT instead of<120 K, depends on the rates of base damage
xation. These rates are governed by an activation energy, which is our next topic.
Hopping
The trapping rate, for both holes and excess electrons, is competitive with the tunneling rate.
This must be the case because DNAis a very eective trap of both holes and electrons; there
are no other materials that are better traps that we are aware of. Thus the way to maximize
trapped radical density is to maximize DNA density, and this is why crystalline DNA tops
the scale in trapping capacity, with trapped radical yields of 0.50.7 Amol/J at 4 K [66,67].
Remarkably, only 3050% of all initial ionizations are lost to recombination. This is re-
markable because tunneling distances, either GuaGua or PyrPyr, are typically short,<
f
7
A
, in all directions [104]. This means that the trapping rate must be fast [k > 10
11
sec
1
exp(1.0 A
1
7 A
)
f
10
9
sec
1
], and the trap depth must be low enough to shut down
tunneling. In order to mobilize trapped charges, an activation energy is required. Charge
transfer governed by an activation energy is referred to as hopping.
Trapping entails dielectric relaxation about the charge altered site. This is analogous to
the Marcus reorganization energy in the liquid state [136]. But in polar solids at 4 K, large
displacements such as molecular translation and rotation cannot occur as a part of the
reorganization. It is constrained to relatively small displacements of the atoms surrounding
the newly charged site. The displacements optimize dipoledipole, dipolemonopole, and
monopolemonopole interactions. The most pliable particles in the DNA matrix (at <120
K) are the protons participating in highly polar bonds (NUHand OUH). Nearly every such
bond in a crystal lattice participates in a hydrogen bond, most notably the NUH
. . .
Oand the
NUH
. . .
N WatsonCrick bonds that zip together the two strands. When a charge attaches
to a particular site, the surrounding hydrogen-bonded protons are relatively free to shift
in response to the newcharge distribution. In the case of hole trapping, this proton shift is so
pervasive that we do not knowof any case where an organic radical cation has been trapped
within a hydrogen-bonded lattice; the radical cations are observed to consistently deprot-
onate. Furthermore, if lattice structure does not provide an opportunity for proton
displacements across hydrogen bonds, the probability of stabilizing the hole decreases
and, if stabilized, it is through carbon deprotonation [137139]. Insight into what makes
DNA such an ecient electron and hole trap has been obtained by studying the annealing
properties of traps.
Annealing DNA irradiated at 4 K leads to a steady decline in EPR signal intensity;
the radical concentration is approximately a monotonic function of temperature. If the
sample is held at any given annealing temperature, the concentration initially decreases and
then plateaus. Detrapping of the radicals is therefore characterized by a large dispersion in
activation energies. This is, in contrast to the annealing properties of a number of
crystalline DNA components, where discrete activation energies can be measured [140
142]. In our working model, the DNAs annealing behavior is explained by three classes of
traps: (a) very shallow, (b) shallow, and (c) deep. The rst two are reversible states and the
third is irreversible.
Very Shallow Traps. It has been proposed that the neutral Gua(N1H)
.
radical,
formed by proton transfer from the Gua
.
+
radical by proton transfer from N1 of Gua to
N3 of Cyt, is a shallow trap [143,144]. This proposal is based on projections from pK
a
made on monomers in dilute aqueous solution, which predict that proton transfer is
favored by 2.3 kJ/mol [22,145]. Ab initio calculations are in excellent agreement with this
value [146,147]. So one expects that an energy of at least 0.025 eV is needed to activate the
return of the proton to N1 Gua, reforming Gua
.
+
. Once Gua
.
+
is reformed, tunneling to
nearby guanines is reestablished as a competitive pathway. Proton transfer therefore is a
gate for hole transfer. Proton-coupled hole transfer describes the thermally driven transfer
of holes from one Gua:Cyt base pair to another.
Charge mobilization is initiated at very low temperatures,<20 K [104]. It has been
proposed that the mobile species at these low temperatures is the guanine-centered hole
[144]. But if activation of hole detrapping entailed only reverse proton transfer, one would
anticipate a relatively discrete activation energy (
f
0.025 eV) and instead a large dispersion
is observed. Detrapping, presumably of holes, occurs from
f
10 to
f
120 K. The energetics
of reorganization (dielectric relaxation) therefore must vary signicantly from site to site.
This observation means that the N1UH
. . .
N3 proton transfer is just one of a large number
of proton shifts. The hydration layer of DNA, even in crystals of DNA oligomers, is
disordered. It is therefore not dicult to envisage a wide range of trapping depths that
depend on not only the energy of proton transfer within the WatsonCrick hydrogen
bond, but also on the proton shifts within the immediate environment.
Shallow Traps. The depth of the traps for the excess electron is expected to be
deeper than the holes. Once more, using the ndings of Steenken [22,145], the change in
free energy for proton transfer can be estimated. In this case, one-electron reduced Cyt
(Cyt
.
) acquires a proton at N3 of guanine via the N3

. . .
HUN1 hydrogen bond, forming
the neutral Cyt(N3+H)
.
radical. Steenken estimates that this transfer is favorable by 20
kJ/mol and this value is also found by ab initio calculations [146,147]. In order to reverse
the proton transfer, at least 0.17 eV is needed. Reversal recreates Cyt
and permits
tunneling to resume. Just like hole transfer, electron transfer is gated by proton transfer.
Proton-coupled electron transfer has been observed in aqueous DNA systems [148].
There is good evidence that the excess electron is mobilized at temperatures between
140 and 180 K. At these temperatures, the Cyt(N3+H)
.
concentration decreases, a de-
crease that correlates with the formation of a neutral radical, Thy(C6+H)
.
, produced by
protonation of one-electron reduced thymine (Thy
)
.
at C6. In order for this to occur, elec-
trons trapped at cytosine must be mobilized [30,49,106]. This increases the probability that
Thy
.
will be formed and, if the temperature is high enough to activate proton addition to
C6, formation of the Thy(C6+H)
.
radical becomes competitive with tunneling. While the
activation energy for electron detrapping shows dispersion, it is less so than for the hole.
This makes sense in that the energy of proton transfer is an order of magnitude larger than
that of the hole. This relatively discrete component would therefore be more dominant
relative to the more disperse contributions to reorganization by the local environment.
Deep Traps. A hole produced by ionization of the sugar-phosphate backbone is
permanently trapped by deprotonation from any of the ve ribose carbons, producing a
neutral sugar radical. The probability that any of the sugar radicals [dRib(C1V H)
.
, etc., in
Fig. 1a] will return to the native structure is very small. This is in part a consequence of
these radicals being relatively stable [142,149151] and in part due to the deprotonation
step being irreversible. The lost proton may attach to water in the hydration shell or to the
DNA bases, e.g., cytosine [30]. Either way, the increased distance between the unpaired
electron and site of altered charge helps protect the radical from recombination events
[137]. The sugar radicals are therefore relatively radiation-resistant. While annealing may
activate unimolecular reactions [150153], the reactions remain centered at the initial site
of hole formation. In this case, the damage is xed at the site of ionization.
The hole formed by ionizations of the backbone, if not trapped by deprotonation,
will transfer to the bases. If the temperature is low enough (<
f
120 K), the hole will be
trapped by guanine in a very shallow trap. But if the temperature is high enough, another
reaction pathway is activated, HO
addition to the guanine radical cation [154]. The

resulting neutral radical may be one-electron oxidized to yield 8-oxoguanine or, in the
absence of an oxidant, lead to formamido-pyrimidine (8oxoGua and fapyGau in Fig. 1b).
While it is not yet known what temperature is required to activate HO
addition, this
reaction is known to occur at room temperature [154].
Thus we nd that the hole is deeply trapped by two distinctly dierent mechanisms.
One that requires no activation energy, sugar radical formation occurs even at 4 K, and
the other that does, HO
addition to the guanine radical cation. Similarly, the excess

electron is irreversibly trapped by two distinct mechanisms, one that is activated and the
other which is not.
A deep trap for the excess electron is the Thy(C6+H) radical. Irradiation of DNA at
temperatures<80 K results in a population of shallowly trapped electrons that consists of
about 80% Cyt(N3+H)
.
and 20% Thy
.
[85,86,155157]. As mentioned above, the

electron is mobilized upon warming to 140200 K. In this same temperature range,
irreversible protonation of Thy
.
at C6 is activated and the excess electron is locked in

place as the Thy(C6 + H) radical [30,49]. Under anaerobic conditions, this radical will
lead to the formation of 5,6-dihydrothymine as a stable end product [158].
An electron trapping reaction analogous to that in thymine might be expected for
cytosine: Cyt
.
+ H
+
!Cyt(C6 + H)
.
(see Fig. 1e for structures). But this reaction is not
observed when DNA, irradiated at<80 K, is warmed [159]. It is presumably quenched by
the faster reaction of Cyt
.
+ H
+
! Cyt(N3 + H)
.
. But a reaction exists by which the
excess electron is deeply trapped by cytosine, and it is not thermally activated. The Cyt(C6
+ H, N3 + H
+
)
.
radical is formed in DNA irradiated at 4 K [144,159]. In addition,
there is evidence of the closely related radical formed by the net gain of hydrogen at C5
of cytosine: Cyt(C5 + H)
.
or Cyt(C5 + H, N3 + H
+
)
.
(the protonation state at N3 is
undetermined). The proposed mechanism for formation of Cyt(C6 + H)
.
invokes spatially
correlated events: electron capture by cytosine accompanied by proton transfer to N3
correlated with the release of a proton by a nearby sugar-phosphate radical cation. Cy-
tosine, thereby, gains one electron and two protons. This radical would be, thereby, a
signature of a clustered lesion. If correct, one would expect to nd two end products, dihy-
drouracil and a single-strand break, in close proximity to one another.
General Scheme
Charge transfer in DNA is summarized by the scheme shown in Fig. 3. Holes on the sugar-
phosphate (SP) tunnel to the nearest base at a rate k
t
in competition with the deproto-
nation rate, k
irr
, forming sugar products (spr
n
). Holes on the bases (B
n
) tunnel between
Figure 3 A working model for charge transfer and trapping in DNA is shown for three deo-
xynucleotides (base B
n
attached to sugar phosphate SP) juxtaposed in space. These deoxynucleotides
may or may not be in the same strand or the same duplex. Hole tunneling occurs from SP to B
n
at a
rate k
t
in competition with the hole trapping rate k
irr
, the rate of deprotonation at one of the sugar
carbons resulting in stable sugar product radicals (spr
n
). Holes transferred to B
n
or holes (excess
electrons) initially formed on B
n
tunnel to other bases at a rate k(n F 1)
t
governed primarily the
through-space distance and the ionization energy (electron anity) of B(n F1). Competing with hole
(excess electron) transfer is reversible proton transfer, forming thermally labile trap sites, B(n FH
+
),
at a rate k
r
. Also competing with hole (excess electron) transfer is irreversible hydroxide (proton)
addition, forming stably trapped base product radicals, bpr
n
, at a rate k V
irr
. Not shown in this scheme
is the fact that the k values for holes are dierent than the k values for excess electrons.
guanines at rate k(n)
t
that depends on the distance to the nearest guanine; otherwise, the
rate is relatively independent of whether the transfer is intrastrand, interstrand, or
interduplex. Competing with hole tunneling between the bases is reversible proton transfer
at a rate k
r
. At low temperatures, the hole is locked in place by this reaction but, if the
temperature is suciently high, back transfer of the proton reenables tunneling. At even
higher temperatures, irreversible reactions (kV
irr
) lead to base products (bp
n
).
The excess electron follows the scheme in a similar way, except that there is no attach-
ment or reaction involving the sugar-phosphate backbone. It attaches to the pyrimidines
where its tunneling rate [k(n)
t
] is controlled by the distance to neighboring pyrimidines and
by the competing reversible proton transfer from guanine to the cytosine radical anion. At
low temperatures, proton transfer shuts down tunneling. At higher temperatures, back
transfer permits tunneling. If the temperature is suciently high, irreversible protonation
terminates transfer, forming base products (bp
n
).
Ultimately, if the end products are formed in clusters, the rates k
irr
and kV
irr
must be
fast relative to k(n)
t
. It will be important to determine these rates.
5. DISTRIBUTION OF STABLE END PRODUCTS IN MODEL SYSTEMS
The ultimate goal is to use our understanding of DNA radiation physics and chemistry to
predict what types of damage will occur in DNA in vivo, including yields and spatial
distribution. A step toward achieving this goal is measuring nonradical (diamagnetic)
damage produced by the direct eect. Until recently, there has been a paucity of information
on direct-type end products because of the diculties inherent to isolating and analyzing
products produced in very small amounts, on the order of 1 part in a thousand. In this
section, we review some of the relevant ndings on stable products produced in directly
ionized DNA, then outline a model by which end product distribution can be linked to our
current knowledge of free radical intermediates and conclude with a fewremarks on howthe
reaction pathways will be inuenced by a chromatin environment.
5.1. High Molecular Weight DNA
Much of the early work on measuring direct damage in DNA focused on cleavage of the
sugar-phosphate backbone, called strand breaks. While strand breaks represent an
important class of products, the specic chemical structure is generally left undetermined.
The importance of this type of lesion is primarily due to the fact that it can be detected
with very high sensitivity and secondarily due to observed correlations with biological
endpoints. High detection sensitivity is a consequence of the fact that strand breaks lead to
large changes in DNA conformation.
Among the earliest work, properties such as viscosity and molecular weight were used
to demonstrate that single- and double-strand breaks are produced by direct ionization and
that these products are inuenced by water content [160]. Progress on the measurement of
strand-break yields accelerated with the discovery by W. D. Taylor that closed circular
DNA (BX174 viral DNA) provided an exquisitely sensitive system for detection of single-
strand (ssb) and double-strand breaks (dsb) [161]. Closed circular DNA adopts a tight
supercoil conformation, which relaxes into an open circle when one strand is broken and
into a linear form when two strands are broken within close proximity (
f
10 base pairs) of
each other. Separation and quantication of these three forms were rst performed by
ultracentrifugation and subsequently by gel electrophoresis.
Products Characterized by a Single-Strand Break
The yieldof single-strandbreaks [G(ssb)] anddouble-strandbreaks [G(dsb)] measuredunder
nitrogen using low LET radiation are summarized in Table 1. The reported G(ssb) is
remarkably consistent considering that these results come from ve dierent laboratories.
The top nine entries report prompt strand breaks. The rst four are for relatively dry DNA,
irradiated at dierent temperatures: 77 K, 6jC, and 25jC. The values cluster tightly around
G(ssb)=0.05 Amol/J. The next ve values are for DNAthat is approximately fully hydrated;
in each case, there is a large uncertainty as to the actual hydration level. It is important
to note that these yields were calculated assuming that only DNA comprises the target
mass; for example, if the sample contains an average of 20 waters (MW=18)/nucleotide
(average nucleotide MW=308), then G(dry DNA)=G(hydrated DNA) (308 +20 18)/
308=2.2 G(hydrated DNA). Inclusion of the counter ion in the hydration layer increases
this factor. Thus if the energy absorbed by the DNA hydration layer is converted to strand
breaks with the same eciency as the energy absorbed by DNA itself, G(ssb) should more
than double in going fromdry to fully hydrated. For hydrated DNA, the observed values of
G(ssb) give an average of 0.07 F 0.02 Amol/J. Using this average, one obtains G(dry
DNA)=1.4G(hydrated DNA), which is consistent with transfer of holes from the
solvation shell to the DNA increasing strand breakage by 40%. If all the holes from the
tightly bound water (G<11) transfer to DNA, as is observed at low temperatures, and 50%
of those holes localize on the sugar so as to give strand breaks, then one would expect an
enhancement of roughly (10/20)0.5, i.e., about a 25%increase due to energy transfer from
the hydration layer. Within this framework of logic, a 40% increase can be explained by
either hole transfer occurring froman even larger sphere of water (G
f
16) or by 80%of holes
localizing on the backbone or a combination of these.
In addition to prompt strand breaks, there are other types of damage that, under
certain conditions, will develop into strand breaks. One such class is alkali labile sites; the
existence of this class of damage is revealed by the early work shown in lines 10 and 11 of
Table 1. Another class involves specic types of base damage that are substrates for
enzymatic repair and, consequently, treatment with the appropriate enzyme results in an
ssb. Entries 1215 compared to 14 showthat the yield of this class of damage is 1 to 4 that of
prompt strand breaks. Yokoya et al. [162] employed endonuclease III (Nth) and formami-
dopyrimidine-DNA glycosylase (Fpg); these enzymes act on products stemming from the
one-electron reduction of cytosine and thymine and one-electron oxidation of guanine,
respectively. These results are discussed further below in the section on base damage.
Products Characterized by Double-Strand Break
In Table 1, we see that the spread in values of G(dsb) is larger than in values of G(ssb).
This is not surprising given the inherent experimental diculties that revolve around
measuring the formation of relatively small amounts of linear DNA in the presence of
large amounts of open circular DNA. These diculties aside, the reported ratios for ssb/
dsb fall primarily in the 1020 range. It has been noted [163,164] that this ratio is much too
small to be accounted for by two ssb occurring independently on opposite strands within
close proximity (about 10 base pairs) of each other. While Boon et al. [163] suggest a
mechanism where base-centered radicals give rise to strand breaks, Ito et al. [164] suggest a
mechanism where localized multiple ionizations result in spatially correlated ssb, resulting
in a dsb. There is now considerable evidence that the base radicals, predominantly
oxidized guanine and reduced pyrimidines, are relatively ineective in causing strand
breaks [98,154], making the later explanation more plausible. Indeed, evidence continues
Table 1 Single- and Double-Strand Break Yields for Low LET Radiation in the Absence of O
2
DNA Conditions
a
G(ssb)
b
(Amol/J) G(dsb)
b
(Amol/J) ssb/dsb Reference
1 .pBR322 Dry/77 K 0.047 0.0014 35 [164]
2 .pBR322 Dry/25jC 0.056 0.0031 18 [164]
3 .pUC18 rh<0.1 (G
f
4)/6jC 0.054 0.0053 10 [162]
4 .pUC18 rh<0.1 (G
f
4)/6jC+37jC 0.047 0.0043 11 [162]
5 .qpBR322 Humid (G
f
20)/77 K 0.034 0.001 33 [164]
6 .pBR322 humid (G
f
20)/298 K 0.120 0.011 11 [164]
7 .pUC18 rh=0.97 (G
f
34)/6jC 0.067 0.0072 10 [162]
8 .pUC18 (G
f
34)/6jC+37jC 0.067 0.0072 9 [162]
9 .pBR322 Frozen aqueous/77 K 0.040.07 1020 [163]
10 .BX174 Alkaline sucrose assay 0.070 0.013 5 [188]
11 .SV40 Alkaline sucrose assay 0.110 0.011 10 [189]
12 .pUC18 G
f
4/6jC+37jC+Nth 0.10 0.0069 15 [162]
13 .pUC18 G
f
34/6jC+37jC+Nth 0.18 0.0171 11 [162]
14 .pUC18 G
f
4/6jC+37jC+Fpg 0.094 0.0103 9 [162]
15 .pUC18 G
f
34/6jC+37jC+Fpg 0.16 0.0193 8 [162]
16 .pUC18 G
f
34/6jC+37jC+Nth+Fpg 0.24 0.0237 10 [162]
a
For the rst two entries, alkaline sucrose gradients were used; all others employed gel electrophoresis. Degree of hydration, deduced from known relative humidity, is given
as G, the molar ratio of water to mononucleotide. Sample temperature during radiation.
b
Yields are based on dry mass of DNA.
to build in favor of dsb arising from two radicals, spatially correlated, on opposing strands
[165].
Complimenting the strand-break studies on DNA irradiated in the solid phase are
studies that use high concentrations of radical scavengers to divide out the indirect from
the direct eect in DNA irradiated in aqueous solution (see Refs. 15, 166, and 167). The
work of Krisch et al. was one of the early studies that provided persuasive evidence that
the direct eect is responsible for about half of the dsb produced under in vivo conditions.
The absolute yields obtained from these cell mimetic conditions, however, are dicult to
compare with the solid-state results.
Production of Strand Breaks by Monoenergetic Electrons and Photons
An incident beam, whether comprised of high-energy photons or fast charged particles,
deposits most of its energy via fast electrons. Because the energy of fast electrons is
dissipated by producing secondary electrons, a large fraction of the radiation chemistry is
due to electrons with very low energies,<20 eV [168]. It is of considerable value therefore
to investigate the eciency by which low-energy electrons create strand breaks.
Pioneering the investigation of strand breaks using monoenergetic electrons, Folkard
et al. [169] discovered that energies<25 eV are sucient to cause ssb, and between 25 and
50 eV, the onset of dsb occurs. They employed pBR322 DNA, under vacuum, spread
approximately as a monolayer. At 50 eV, the eciency for ssb/dsb is 2.0; it climbs to 5 for
100500 eV, and it plateaus around 10 for 20004000 eV. More recently, the energy of
electron beams has been extended down to 3 eV by the Sanche laboratory, measuring ssb
and dsb in plasmid DNA under ultrahigh vacuum [68,170,171]. Surprisingly, strand
breaks are observed in substantial yields even at energies below ionization thresholds,
1.510 eV. At energies below 20 eV, the authors provide convincing evidence that
dissociative electron attachment (DEA) is the major pathway for producing a wide range
of damage, including ssb and dsb. Just what fraction of strand breaks, under in vivo
condition, is due to DEAvs. one-electron oxidation is an important question that remains to
be answered.
Hieda and Ito [172] measured strand-break yields as a function of monochromatic x-
ray energy, using 2.146, 2.153, and 2.160 keV, corresponding to below, on, and above the K-
edge for phosphorus. While the eciency of single-strand breaks did not vary signicantly,
the eciency of double-strand breaks did increase by about 30% at the K resonance peak.
These authors raise the possibility that dsb eciency is enhanced by an Auger cascade in
phosphorus. The enhancement of dsb/ssb by resonant excitation of phosphorus provides a
method for assessing the relative contribution of the direct eect to biological endpoints such
as cell death and mutation [173].
Products Derived from the DNA Bases
The formation and identication of the free bases, and subsequently other types of base
damage, have been reported by Swarts et al. [101,174176]. These papers present the rst
measurements of specic products produced by the direct eect in DNA. Equally im-
portant, the sample type and preparation correspond closely to that employed in a wide
range of EPR studies that identify free radical intermediates trapped on DNA [14,30,83].
The free bases (thymine, cytosine, adenine, and guanine) are the simplest form of
product in this class. But the simplicity of these chemical products belies the complexity of
their origin. The yield of each free base was measured using HPLC on salmon sperm
DNA, variably hydrated (2<G<33), subjected to g-irradiation at RT under N
2
or O
2
, and
subsequently dissolved in water [101]. Focusing on the N
2
results, the yield of all four
bases combined holds relatively constant in the hydration range 2<G<33 (0.050.07
Amol/J,) where the G values are based on the weight of DNA plus its hydration shell. In
order to compare these values with those above (Table 1), one needs to recalculate these
based on the dry weight of DNA, which gives a plateau of 0.060.07 Amol/J for 2<G<13
and then climbs to 0.17 Amol/J at G=33. The yields for free base release therefore correlate
well with the ssb yields shown in Table 1, entries 19. Since it is well known that in dilute
aqueous solutions, free base is released as a consequence of radical formation on the
sugar-phosphate backbone [177], it is likely that some (or perhaps all) of the released bases
are derived from sugar-centered radicals. When Swarts et al. analyzed the yields of each of
the free bases separately, they found Gua to be about 60% that of Thy, Cyt, and Ade, with
the yields of the latter three being the same. It is important to reconcile this with the
observation that in crystalline deoxynucleotides [98], the yield of guanine is not reduced
relative to the other three bases, but when DNA is irradiated in dilute aqueous solution
[178], the yield of guanine is reduced. One possibility is that in high molecular weight
DNA, both solid and in dilute solution, the radical formed by hydrogen abstraction from
C4Vis the predominant sugar-centered radical. The C4Vradical undergoes fast h-elimination
of the 3V phosphate, forming an enolether radical cation [179] which is capable of
oxidizing an adjacent guanine via electron transfer [180]. Such an electron transfer would
prevent release of guanine as a free base. Additionally, one must propose that in crystalline
oligodeoxynucleotides, either hydrogen abstraction from C4V is not predominant or 3V
phosphate h-elimination is inhibited.
Swarts et al. [175] measured the yields of 14 base end products in addition to the free
bases. For 2<G<13, the yields (based on total weight) are relatively constant and are
largest for 8-oxoGua (0.0840.101 Amol/J), FapyGua (0.0120.021 Amol/J), and 5,6-
diHThy (0.0260.067 Amol/J). This result is consistent with holes and electrons produced
in the tightly bound water transferring to the DNA and creating the same spectrum of
products, at approximately the same yields, as for holes/electrons formed by direct
ionization of the DNA molecule. The ratio of yields for products stemming from one-
electron oxidation vs. one-electron loss is unexpectedly large: 0.201/0.028, 0.158/0.068,
and 0.150/0.052, for G of 2.5, 10.3, and 13.2, respectively. Since this ratio is expected to be
close to 1.0, the authors conclude that a large fraction of the reduction products were not
detected. The authors present a working model for oxidation product formation by direct
eects in DNA that combines their ndings with the preexisting knowledge on free radical
intermediates. This model, representing a major advance in the eld, proposes that (1) hole
transfer from the sugar-phosphate backbone to the bases competes with damage local-
ization on the sugar, (2) damage localized on the sugar will give rise to a free base, (3) holes
transferred to the base stack are trapped preferentially by guanine, and (4) irreversible hole
trapping occurs primarily by OH
addition. We build on this model in Sec. 5.3 below.

Clustered Damage
One type of clustered damage is double-strand breaks, consisting of two single-strand
breaks in close proximity to one another. Since techniques for measuring dsb have been
available for some time, a fair amount of data is available, as summarized above. But until
recently, there has been very little experimental information on other types of clustered
damage produced by direct eects. The work of Yokoya et al. extends our knowledge to
clustered damage consisting of one base damage in close proximity to either a strand break
or another base damage on the opposing strand. Yields of dsb are compared with the
yields of clusters containing base damage. They employ the Nth enzyme to create a strand
break at sites containing 5,6-dihydrothymine, thymine glycol, and abasic sites and Npg to
create breaks at 2,6-diamino-4-hydroxy-5-N-methylformamidopyrimidine, 7,8-dihydro-8-
oxo-2deoxyguanine, and apurinic sites. Comparing lines 8 and 16 in Table 1, it is seen that
treatment with both enzymes raises the ssb and dsb yields by about 3. The value of 0.024
Amol/J (based on dry DNA weight at g=34) represents one of the best measures to date
for the yield of clustered damage, 1/3 due to the dsb type and 2/3 due to base-damage-
opposed-to-ssb-or-base-damage type. Since the yield of total clustered damage is almost
certainly signicantly larger, we see that the probability of producing clustered damage by
direct eects is comparable to that of producing ssb.
5.2. Oligodeoxynucleotides
DNA samples consisting of oligodeoxynucleotides provide better-dened samples for
investigating the inuence of variables such as base sequence, conformation, degree of
hydration, chemical environment, and DNA packing density. This is particularly true if
the oligomers are in crystalline form where these variables are dened with atomic
precision. When high molecular weight DNA is condensed, the packing density tends to
be highly heterogeneous and dicult to reproduce from sample to sample [91,92].
Crystalline DNA reduces this variability dramatically, making it possible to measure free
radical yields with a typical precession of F10% [66]. This kind of reproducibility, which is
a direct consequence of the sample homogeneity, when coupled with atomic resolution
knowledge of sample structure, provides a powerful system for investigations of DNA
radiation physics and chemistry.
Free Base Release
The yields of free base from crystalline oligodeoxynucleotides were measured by Razska-
zovskiy et al. [98]. Three types of crystals, d(GCACGCGTGC)
2
, d(CACGCG):d
(CGCGTG), and d(CGATCG)
2
:2D(D=daunomycin or adriamycin), were x-irradiated
(70 keV) at 4 K, warmed to RT, dissolved in water, and released base analyzed using
reverse phase HPLC. Free radical yields were measured on the same samples, prior to
dissolution, using EPR at 4 K. The yield (based on total weight) of the combined four bases
ranges from 0.06 to 0.11 Amol/J, 1020% of the yield for total free radicals trapped at 4 K
(prior to annealing). The fact that the intercalated anthracycline moiety of daunomycin
eectively scavenges all the holes and electrons from the bases [105] eliminates base-
centered radicals as precursors to base release. The observation that hydroxyl radicals are
not trapped in the crystalline matrix rules out hydroxyl radical reactions. It is concluded,
thereby, that radicals xed on the sugar are precursors to base release. This strongly
suggests that direct ionization of the sugar-phosphate backbone is followed by deproto-
nation of the primary radical cation and that deprotonation competes with hole transfer
from the radical cation to the bases. From this result, the yield of DNA strand breaks for
DNA hydrated in the 4<G<14 range is predicted to be
f
0.1 Amol/J.
Strand-Break Products
By employing crystalline DNA, the rst measurements of specic strand-break products
were possible [97,99]. Crystalline d(CGCG)
2
, d(CGCGCG)
2
, d(CACGCG):d(CGCGTG),
and d(CGCACG:CGTGCG) were irradiated at 4 and 293 K, dissolved in water, and
analyzed with anion exchange HPLC. The major products were free bases and oligodeoxy-
nucleotides with 3V - and 5V -phosphate end groups. Based on just the later products, the yield
of immediate strand breaks varies from 0.06 to 0.16 Amol/J. There is increased damage to
the terminal sugars relative to the internal sugars, perhaps reecting the presence of a free
OH group in the terminal sugars (none of the oligomers are phosphorylated at the
termini). Accumulation of strand-break products is remarkably resistant to dose satu-
ration, remaining linear out to doses of
f
500 kGy. This is consistent with a neutral sugar
radical as the precursor to strand breaks. In addition, strand-break yields are not aected
greatly by sample temperature during radiation exposure. Most striking is that there is no
obvious preference for the cleavage at Ade, Thy, Cyt, or Gua. The lack of inuence of the
base ionization potentials can be explained by the high exothermicity of the process,
making hole transfer from the sugar-phosphate radical cation independent of the base
itself. Prediction of the DNA strand-break yields (4 < G < 8 for these crystals) is also
f
0.1 Amol/J.
In general, it appears dicult to correlate the results obtained using vacuum-UV
with those obtained using high-energy ionizing radiation. We should note, however, that
when vacuum-UV is used to directly ionize deoxyoligonucleotides in solid form, a
dependence on base sequence is observed [181]. In order to explain the observed products,
these workers proposed that an initial site of damage is the deoxyribose moiety.
Sugar Radical Intermediate
If sugar-centered radicals are indeed the primary precursors to strand breaks, then one
should be able to observe these with EPR. But EPRdetection is dicult because the diversity
in radical structure and conformation tends to make the spectrum broad, with poorly
resolved hyperne structure and much of the signal masked by the more intense signal from
the base radicals [20,96]. To some degree, these problems can be overcome by applying EPR
to study a single crystal of DNA. This has been done for crystals of d(CTCTCGAGAG)
2
where x-irradiation at 4 Kis shown to produce a radical due to the net loss of hydrogen from
C3V . The yield of the C3Vradical is 0.03 F 0.01 Amol/J. It does not dose-saturate up to 100
kGy, and it makes up about 4.5% of the total radical population trapped at 4 K. Since this
study does not exclude formation of sugar radicals at the other four carbon sites, this
observation ts nicely with projected strand-break yields of
f
0.1 Amol/J.
Other Precursors to Strand Breaks
Although a reasonably good correlation exists between the yield of trapped sugar radicals
and the yield of strand breaks, this does not prove that sugar radicals produced by direct
ionization are the only, perhaps not even the predominant, precursor to strand breaks. As
discussed above, Sanche et al. have proven that low-energy electrons (<20 eV) produce
strand breaks in plasmid DNA by dissociative electron attachment (DEA). This work has
been extended to studies of low molecular weight fragments produced by monoenergetic
electrons with energies from 1 to 30 eV [182185]. A series of pyrimidine oligodeoxy-
nucleotides {d(T
6
), d(T
12
), d(C
6
), d(C
12
), d(T
9
), d(C
9
), d(T
6
C
3
), d(C
3
T
6
), d(C
6
T
3
)} were
chemisorbed onto a gold substrate via a thiol modication at the 3V -end and exposed to the
electron beam under ultrahigh vacuum. The major fragments are CN, OCN, and/or
H
2
NCN, and when Thy is present, there is a small contribution tentatively assigned to
CH
3
CCO. One of the main conclusions is that, for incident electrons with<20 eV,
fragmentation occurs at the bases through DEA, in contrast to >20 eV where fragmen-
tation is controlled by nonresonance processes. Another is that base fragmentation in
single-stranded DNA depends on base type and sequence. A challenge for future work is
to determine the degree to which these processes play a role in solid-state DNA when
ionization is initiated at high energies in the absence of the vacuum and metal interfaces.
Currently, it is dicult to reconcile the base ring fragmentation products and properties
such as sequence dependence with the lack of evidence for such events from studies using
EPR and HPLC. One possibility is that the resonance states that yield these fragments are
quenched in bulk samples and electron capture by the pyrimidines dominates. This
remains to be tested.
5.3. A Working Model
Oligodeoxynucleotides, Crystalline Samples
A model that is consistent with the observed free radical intermediates trapped in
crystalline deoxyoligonucleotides x-irradiated at 4 K and warmed to RT has been pub-
lished [144]. Here we review the salient points of that model and then extend it to other
types of DNA samples.
The crystal-based model assumes that half of the radicals trapped at 4 K are derived
from one-electron loss and the other half from one-electron gain. Following thermal-
ization, electrons are captured exclusively by the bases and the holes are distributed
according to electron densities of each component: bases, sugar-phosphate backbone, and
solvation shell. Holes initially formed in the tightly bound solvation shell of DNA rapidly
transfer to the sugar and bases [67,93]. Because all of the end products are assumed to
come from free radical precursors [143], possible damage from excitations and dissociative
electron attachment [170,183] are excluded. There are predominately ve radical types
produced by electron loss or electron gain: one-electron oxidized sugar phosphate (SP
.
),
guanine radical cation (Gua
.
+
), cytosine radical anion (Cyt
.
), thymine radical anion

(Thy
.
), and, perhaps, adenine radical anion (Ade

.
). These radicals, with the possible

exception of Thy
.
, are unstable at 4 K. Reversible proton transfer, across the Watson

Crick hydrogen bond, stabilizes the hole at Gua and the excess electron at Cyt and Ade
[22]. Irreversible deprotonation from the sugar-phosphate backbone traps out ve dier-
ent radicals due to the net loss of hydrogen from each of the ve deoxyribose carbons (Fig.
1a). The protons released by the one-electron oxidized sugar phosphate directly (or
indirectly) promote proton addition to carbon sites of the base radical anions, yielding
base radicals that are irreversibly protonated [30,159]. At 4 K, the ratio of hole trapping at
guanine vs. SP is
f
76:24 and the ratios for electrons trapping at Cyt/Thy/Ade is
f
86:8:6.
The base-centered radicals are thermally more labile than the sugar-centered radicals.
The model proposes that the deprotonated guanine radical cation [Gua(N1H)
.
] is the
shallowest trap, possessing an activation energy with large dispersion. Thus hole detrapping
occurs between 4 and
f
140 K. Back transfer of the proton is thermally activated, creating
Gua
.
+
and opening the gate for tunneling to other guanines in close proximity [186]. In a
crystal lattice, where the guanineguanine intermolecular distances are comparable to the
interstrand and intrastrand distances [104], the mobilized hole undergoes a random walk in
three dimensions. Given sucient thermal energy, the hole continues its walk until it
recombines with another radical or it is irreversibly trapped by OH
addition [154]. Under

gradual annealing conditions, recombination predominates. After annealing to 120 K, the
radical population consists primarily of H-addition to C5C6 of cytosine, H-addition to C5
of thymine, H-addition to C5/C8 of adenine, and H abstraction from sugar. The relative
concentration of these is approximately 0.3:0.1:0.1:0.5, respectively. Evidence for the rst
two radical types comes fromsingle-crystal EPR[94]; evidence for the third is based on work
on reduction of adenine in monomeric and oligomeric systems [85,95,98,187], and evidence
for the fourth comes from the yields of end products [97,98] related to sugar damage.
Continued annealing from140 to 240 Kdetraps the excess electron by reforming Cyt
.
; this
mobile state of the excess electron is formed by back transfer of the proton, from N3 of
cytosine to N1 of guanine. The electron walk is terminated by combination reactions with
base-trapped radicals or by irreversible protonation at the C5C6 bond of cytosine or
thymine. These later reactions are relatively minor because once permissive temperatures
(>140 K) are reached, the concentration of Cyt
.
has been reduced signicantly by

combination reactions [144].
The proposal that holes are detrapped at lower temperatures than the excess
electrons is based on the observations discussed above in Very Shallow Traps and Shallow
Traps (Sec. 4.3.2). One expects that the activation energy needed to detrap the hole from
Gua in duplex DNA is relatively small, an order of magnitude less than that needed to
detrap the electron. This ts well with the observation that upon warming 4 K irradiated
crystalline DNA to 77 K, 1030% of the radicals anneal out, i.e., at least one of the
trapping sites [de infra Gua(N3H)
.
] is very shallow.
From the yields of 5,6-dihydropyrimidine radicals, we predict reduction product
yields of 0.040.06 Amol/J for 5,6-dihydrouracil and 0.030.05 Amol/J for 5,6-dihydro-
thymine for B-form DNA hydrated to 9 waters per nucleotide. With respect to oxidation
products, we predict strand-break yields
f
0.10 Amol/J. A very surprising prediction of this
model is that the yield of damaged guanine is nil. Half the damage is oxidized sugar
products and the other half is reduced pyrimidines.
High Molecular Weight DNA, Amorphous Samples
Samples of high molecular weight DNA are generally amorphous; the local chemical
environment is heterogeneous and dicult to characterize. The heterogeneity and lower
DNA packing density of the amorphous samples are believed to be important factors with
regard to understanding the dierences between direct eects in amorphous vs. crystalline
DNA samples. Packing density reects the global average of the interhelix distances. When
this distance is short, the DNA scavenges a larger fraction of the radicals created in the
solvent compartments. Higher scavenging reduces radical recombination and results in a
higher yield of DNA-trapped radicals. Variable packing density has been evoked to explain
the threefold variation in free radical yields for DNA lms having the same average value
for G [91,92]. It was also used to explain why the yield of trapped radicals for DNA in the
amorphous state is about 1/2 that of the crystalline state [66]. Note that across this range of
DNA samples, the yield of radicals that are initially trapped varies by a factor of 3 to 6 even
if variables such as G, base sequence, and conformation are held constant.
The events that occur after initial trapping should also be governed by the interhelix
distance. Given that the tunneling rates are strongly dependent on distance and relatively
independent of what occupies the intervening space [118120], the average rate of inter-
molecular hole/electron transfer should be much slower in amorphous DNAcompared with
crystalline DNA. Therefore the random walk in amorphous samples tends toward one-
dimensional, in contrast to that in crystals where it is known to be three-dimensional [104].
The dimensionality of the walk will inuence the probability of radical recombination. Since
tunneling is temperature-independent, this will inuence the yield of trapped radicals even at
4 K. This eect will also inuence the rate of radical recombination when the DNA samples
are annealed.
Another consequence of increased interhelix distance is related to diering DNA
scavenging capacities for electrons vs. holes. In the G<10 range, electrons and holes
produced in the solvent layer are scavenged by DNA with equal probability. For
9<G<30, electron scavenging capacity changes very little while hole scavenging drops
rapidly to zero [92]. As a result, we expect that the stoichiometry of trapped holes to
trapped electron be
f
50:50 in crystalline DNA [144] and
f
40:60 in amorphous DNA
[14,30]. When coupled with the dimensionality of the walk, this should have signicant
consequences on the distribution of end products derived from base radical intermediates.
In crystalline DNA irradiated at 4 K and annealed to RT, the model predicts that at
low temperatures (40140 K), the guanine radical cation undergoes a three-dimensional
walk. If the range of holes is large, termination by combination with Cyt(N3+H)
.
radicals
has a high probability. The net result is that damage to guanine is quenched and the
remaining reductive damage to the pyrimidines will be about the same as the yield of sugar
damage (strand breaks). In contrast, amorphous DNA irradiated at low temperatures
contains a larger imbalance between holes and electrons on the base stacks. If 85% of the
holes are trapped by guanine, it means that 34% (0.8540%) of all radicals are due to
one-electron oxidized guanine while 60% are due to one-electron reduced pyrimidines. If
the range of the mobilized hole (or electron) is large during an anneal to RT, there should
be very little oxidized guanine products and the yields of reduced pyrimidine products
should be about twice the strand-break yield.
Impact of Sample Temperature During Irradiation
Much of the information on direct damage to DNA comes from EPR studies of free
radical intermediates that are, out of necessity, trapped by irradiating samples at low
temperatures. In order to predict the biological consequences of direct eects, that
information must be extrapolated to sample irradiation at room temperature. In doing
so, there are at least 10 competing reactions to consider: (1) hole transfer from the solvent
shell to the DNA, (2) hole transfer from the sugar-phosphate backbone to the bases, (3)
hole transfer between bases, (4) electron transfer between bases, (5) rate of deprotonation
of the solvent hole (HO
.
formation), (6) reversible proton transfer between the base pair of
the trapped hole, (7) reversible proton transfer between the base pair of the trapped
electron, (8) irreversible proton transfer from the sugar phosphate-centered hole, (9)
irreversible proton transfer to pyrimidine radical anions, and (10) irreversible hydroxide
addition to the guanine radical cation. Extrapolation to room temperature comes down to
what is known about the rates of these reactions at room temperature. Although some of
the parameters are known, such as the two values for hole and electron tunneling, most are
unknown, such as the frequency factors for the tunneling reactions and activation energies
for the thermally activated reactions. However, based on temperature stabilities of various
intermediates and a small amount of data on samples irradiated at variable temperatures,
some educated guesses can be made.
The yield of strand breaks appears to be relatively independent of sample irradiation
temperature, as discussed above. This implies that competing processes do not have much
impact on reactions 1, 2, 5, and 8. That is, the competitions between holes tunneling from
the solvent to DNA and deprotonation of H
3
O
.
+
and between hole tunneling form the
sugar phosphate to the bases and deprotonation of the sugar are fairly temperature-
insensitive (from 4 to 300 K). In contrast, the mobility of the holes and excess electrons
centered on the bases is very temperature-sensitive, zero at 4 K, onset at
f
40 K, and
highly mobile at 180 K. By our model, the mobility is controlled by the proton transfer
rate across the base-pair hydrogen bond. Based on the temperatures for mobility onset, the
activation energy is relatively low and therefore at RT, the hoping rate for both holes and
excess electron must be appreciable (as observed). Competing with the base-to-base hole/
electron transfer reactions (3, 4, 6, and 7), there are irreversible reactions (9 and 10) that
lock out the damage site. The activation energy for reaction 9 is almost certainly less than
that of reaction 10. We expect therefore that the range of the excess electron will be shorter
than that of hole. The shorter the range, the less likely recombination will occur, favoring
higher yields. The yield of base damage therefore should increase with increasing sample
irradiation temperature.
Based on the above, we make the following predictions for direct damage in DNA
irradiated at 297 K compared to 4 K (in the absence of oxygen). (1) Prompt strand-break
yields will be about the same,
f
0.1 Amol/J. (2) Oxidized guanine products increase
substantially; yields become comparable to, or higher than, that of prompt strand breaks.
(3) Reduced pyrimidine products increase substantially with yields greater than or equal to
the sumof the yields for prompt strandbreaks andoxidizedguanine products. (4) The ratioof
base damage to prompt strand breaks will be between 2:1 and 4:1 (compared to 1:1 for 4 K).
5.4. Extrapolation to Chromatin DNA
A full understanding of the radiation chemistry of DNA in vivo requires an understanding
of how the cellular environments of DNA modify the events discussed above. While the
most common environment is that of DNA at rest in tightly packaged chromatin, it is
important to consider the environment when DNA is being translated and transcribed.
Also, the environment surrounding mitochondrial DNA diers from that of nuclear
DNA. The inuence of these in vivo environments is likely to be considerable. While this
area has been researched by a number of laboratories in the past, this area is poised for
rapid progress due to the new array of molecular biological tools that improve our ability
to dissect the relevant parts of the living cell. While we have not covered such topics as
DNADNA and DNAprotein cross-links, this is not because we view them as unim-
portant. Rather, we believe it is premature to try to integrate this information with that on
systems containing DNA in isolation.
6. SUMMARY
This review has looked at the direct eects of ionizing radiation on nucleic acids. The rst
step was to review detailed EPR/ENDOR experiments on irradiated model compounds at
low temperatures in order to study the primary radiation-induced defects. Next, it was
shown how these EPR spectra are used to simulate the EPR spectra of the DNA polymer.
A section on track expansion and charge mobility covered the processes by which
excess electrons and holes move through DNA, and what reactions compete with charge
transfer. Current work on determining the conductivity of DNA is discussed. Based on the
high yields of radiation damage products in DNA, it is concluded that DNA is an
insulator. Next, the protonation/deprotonation schemes are discussed, which can account
for the types of free radicals that are trapped in DNA. A general scheme is presented to
summarize charge transfer in DNA.
A discussion of the distribution of stable end products produced by direct ionization
in DNA is presented. Single- and double-strand break yields for low LET radiation are
discussed. Then work on end products derived from the DNA bases is reviewed. Recent
work on oligodeoxynucleotides, including free base release, strand-break products, and
sugar radical intermediates, is summarized. Finally, a model for end product formation by
direct eects in DNA, based on the knowledge of free radical intermediates, is presented.
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16
Photon-Induced Biological Consequences
Katsumi Kobayashi
High Energy Accelerator Research Organization
Tsukuba, Japan
1. INTRODUCTION
In this chapter, recent research on photo- or radiobiological phenomena is reviewed in
which the underlying processes are considered to be initiated from specied photoabsorp-
tion events in biologically relevant atoms or molecules. The energy range of photons
covered in this chapter is above 5 eV. Therefore synchrotron radiation (SR) is a key word
in the chapter. Molecules or samples reviewed in this chapter are mainly restricted to
biologically relevant molecules or living cells. Because of the complexity of these samples,
entire mechanisms from photoabsorption to biological consequences have not been eluci-
dated in most cases, and much remains to be studied in the future. Because earlier studies
published before 1990 have already been reviewed elsewhere [13], most of the referred
papers in this chapter are those after 1990. Also, many vacuum ultraviolet (VUV) studies
appeared in Photochem. Photobiol. Vol. 44, No. 3 (1986), which is a special issue dedicated
to VUV work. What characterize this chapter are samples, which include biomolecules,
water, and living cells.
Photons induce various types of changes in molecules. Photon-induced molecular
processes, and hence molecular products, depend on the energy of the illuminating
photons, reecting the amount of absorbed energy. When a molecule is a constituent of
a biological system, such as living cells, photoabsorption can cause various types of
biological eects. One of the most well-known examples of photon-induced biological
eects might be the sterilizing action of ultraviolet light (4.88 eV or 253.7 nm) from low-
pressure mercury lamps. This mechanism has been well studied for many years, and has
been well understood. For further details concerning these phenomena, see review articles,
e.g., Ref. 4. The purpose of this chapter is to review the action of photons, the energy of
which is higher than the UV light from a germicidal lamp, namely, from 5 eV to the x-ray
region. X-rays or g-rays are also known to induce various biological eects. However,
these actions of radiation are understood to be initialized mainly through energy transfer
from secondary electrons to the biological molecules including water. The amount of
energy transferred to molecules from electrons cannot be specied in most studies. These
radiobiological studies are not described in this chapter. Studies in which the amount
transferred to molecules was specied by the method of illuminating monochromatic
photon beams to the biological system, and studies in which the photon energy depen-
dence was observed as the result of specic photoabsorption events, are described in this
chapter. To study the photon energy dependence, monochromatic photon beams are
needed over a wide energy range, including ultraviolet (UV), vacuum UV, and a higher-
energy region up to x-rays. Only a light source having a continuous spectrum in such a
wide spectral range with practical intensity would be synchrotron radiation (SR). Recent
studies with biologically relevant atoms or molecules and with living cells using SR as light
source are introduced.
When we consider that probability of energy transfer from electrons to molecules
(inelastic scattering) is closely related to the absorption spectrum of the molecule, we
would soon realize that photobiology in the vacuum UV and soft x-ray regions would
greatly contribute to our understanding radiobiological processes. Photoabsorption spec-
troscopy is very important because photoabsorption is the rst step in the whole process
leading to biological consequences.
2. IRRADIATION SYSTEM WITH SYNCHROTRON RADIATION
Presently, more than 20 synchrotron facilities are working or under construction in the
world. Synchrotron radiation generated from electron storage rings is introduced into the
experimental area situated around the ring through beamlines. Most of the beamlines are
equipped with monochromators to monochomatize the white radiation. These beamlines
are usually optimized for high-resolution spectroscopy. When we wish to study photo-
chemical reactions, a suciently high ux is required to produce enough product for
detection. A high ux is usually not consistent with a high resolution. Beamlines with a
sucient ux should be constructed with a reasonable compromise concerning the
resolution. It should also be noticed that a wide beam is often necessary to uniformly
illuminate a sample, because it sometimes happens that only a small fraction on the
surface can absorb photons in a thick sample because of the large absorption cross section
in the vacuum UV region. One method to fulll both requirements is to accommodate two
sample positions in the beamline, one at the focal point for a high ux density, the other at
an o-focal point for a wider and more uniform beam [5].
There were only a very few beamlines where these requirements were taken into
consideration. The rst vacuum UV beamline dedicated to photobiological research was
constructed in 1980 at Synchrotron Radiation Laboratory, University of Tokyo at Tana-
shi, Tokyo [6]. X-ray beamlines for radiobiology were constructed at the Photon Factory,
Tsukuba, Japan [7], after some experience concerning monochromators and irradia-
tion apparatus. These beamlines were optimized for irradiation. At the Photon Factory,
supporting facilities for radiobiological experiments were also constructed near the
beamline, which is essential for visiting radiobiologists to perform experiments in good
condition.
In the UV and vacuum UV regions, the eciency of the biological eects is usually
evaluated based on the incident photon. The eciency is expressed in units of m
2
, and is
usually called the action cross section. Another denition used to evaluate the eciency is
based on the absorbed energy, and is expressed in Gy
1
(=kg/J). This is commonly used
in radiobiology. In this chapter, the word eciency is used based on the incident photon,
except when particularly described, because the interactions of photons with molecules are
neglected when discussed using Gy.
3. EFFECTS ON DNA AND ITS CONSTITUENTS IN THE DRY STATE
3.1. Vacuum Ultraviolet Region
DNA molecules have now become very familiar, not only to scientists, but also to
nonscientic people. However, it is surprising that the photoabsorption cross section of
this molecule has not yet been measured over the whole energy region. A direct measure-
ment of absorption by the transmission method is dicult because of the large absorption
coecient in the vacuum UV region. The absorption spectrum calculated from exper-
imentally obtained optical constants is so far available only below 82 eV by Inagaki et al.
[8]. In 1986, using synchrotron radiation, the absorption spectrum of DNA was obtained
using a photoacoustic technique [9].
The energy of 253.7 nm (4.9 eV) photons is not large enough to ionize a DNA mole-
cule, because the ionizing potential of organic molecules lies around 8 eV. In the vacuumUV
region, we can see the transition from excitation to ionization in the photon energy depen-
dence of biological phenomena. Below 8 eV, the production cross sections of cissyn type
and (64) photoproduct type thymine dimers were measured in the energy region between
4.3 eV (290 nm) and 8.3 eV (150 nm) using sublimed lm of thymine as a sample [10]. The
authors reported that both action spectra of these products are similar, and that the quan-
tumyields stay almost constant above 200 nm, 0.008 and 0.013, respectively, but decrease by
about half at 150 nm. This suggests that the mechanismto formdimers is independent of the
energy of the photon illuminated, and that another reaction channel may open when excited
with higher-energy photons. Similar results were also obtained with a DNA molecule using
an enzyme-linked immunosorbent assay to detect thymine photodimers [11].
When higher-energy photons are illuminated to DNA, another type of damage
begins to emerge, which is breakage of the DNA main chain consisting of deoxyribose and
phosphate; in other words, strand breaks of DNA. Because of the double-helix structure
of DNA, these are classied into two types, single strand breaks (ssb) and double strand
breaks (dsb). Hieda et al. [12] extended their earlier work [13] on strand break induction in
plasmid DNA up to 20.7 eV (60 nm). They demonstrated that photons of 8.3 eV (150 nm)
can induce double strand breaks in DNA, and that the induction cross section of dsb
increases with an increase of the photon energy more rapidly than that of ssb induction.
Although the strand breaks of DNA have been commonly observed, there have been very
few studies on the chemical nature of the cleaved edge. Ito and Saito [14] studied the edge
structure of strand breaks induced by vacuum UV, using oligonucleotides as model
compounds of DNA. It was demonstrated that, on illumination by VUV photons, strand
breakage of DNA is a result of the destruction of deoxypentose, releasing a free base not
of the simple breakage of a phosphoester bond. They also discussed the base dependence
of the breakage eciency [15]. Saito and Hieda [16] succeeded to demonstrate this
transition from UV type, base damage, to strand-break-type damage using thymidylyl-
(3V!5V)-thymidine (dTpdT), with an increase of the photon energy from 4.1 eV (300 nm)
to 8.3 eV (150 nm). The action cross sections of UV-type damage was larger than that of
strand-break-type damage when the photon energy was less than 5.9 eV (210 nm); above
this energy, UV-type damage became the minor fraction.
Recently, a group in the United Kingdom started to study the eect of vacuum UV
photons using the Daresbury synchrotron facility. They measured the yields of ssb and dsb
in plasmid DNA, and proposed that the mechanism or a precursor to produce both types
of strand breaks are common, because the photon energy dependence is similar for both
types, although the absolute yield diered by 50-fold [17]. They conrmed that double
strand breaks could be induced by low-energy photons of 7 eV, as had been reported by
Hieda et al. [12]. From an energetic point of view, this observation would be a great
challenge to theoretical radiobiologists, who usually assume that about 20 eV is the
minimum energy to induce double strand break.
3.2. Soft X-Ray Region
Soon after commissioning of the Photon Factory, KEK Japan, the K-shell resonance
photoabsorption by a phosphate group in a DNA molecule was found, and the eect of
phosphorus photoabsorption has been studied using various samples [18,19]. Inner-shell
photoabsorption by phosphorus has attracted much attention from two reasons: (1) inner-
shell photoabsorption is followed by the Auger eect, which emits Auger electrons and,
consequently, a multiply charged atom or molecule is produced, and (2) phosphate
constitutes the main chain of a DNA molecule together with deoxyribose. Also practically
important is that the absorption cross section at this resonance is about vefold of the o-
resonance K-shell absorption cross section. Therefore we can expect ecient photo-
absorption by phosphorus in DNA, and hence, an ecient production of strand breaks by
illuminating on-resonance x-rays. The true eect of phosphorus photoabsorption can be
deduced by comparing the eciency by monochromatic soft x-rays at the resonance
absorption (2153 eV) with that of o-resonance x-rays (2147 eV), because the resonance is
so sharp that 2147-eV x-rays cannot be absorbed by the K-shell of phosphorus.
Ito et al. [20] studied the mechanism to produce strand breakage by phosphorus
photoabsorption using a dinucleotide as a sample, and revealed that even with photo-
absorption by phosphorus strand breakage occurs through the destruction of deoxyribose
of the 5V end, leaving adenine and 5V-AMP as products. Yamada et al. [21] used penta-
deoxythymidylic acid (d(pT)
5
) as a sample, and analyzed the products quantitatively with
on-resonance (2153 eV) and o-resonance (2147 eV) x-rays. They found that the distribution
of the products was independent of the x-ray energy, and that the yields of the products were
proportional to the absorption cross section of the sample. Unexpectedly, they could not
nd any evidence of Auger-specic products, neither qualitatively nor quantitatively.
The yields of single and double strand breaks were studied with plasmid DNA at ve
specic photon energies around the K-shell absorption edge of phosphorus, including the
on-resonance energy. The yields of ssb and dsb were parallel with the absorption spectrumof
DNA. It was found that the yield of double strand breaks per absorbed energy in the sample
was higher at the on-resonance photon energy than at o-resonance, while the yield of single
strand breaks was independent of the photoabsorption site [22]. Because the prepared
plasmid samples were in the solid state, such as a pellet, plasmid molecules are closely
packed, neighboring with each other. Under this circumstance, photo- or Auger electrons
generated at one molecule can hit other molecules nearby, which may cause an increase in
the yields of strand breaks. In a following study, they prepared a plasmid sample buried in an
overwhelming amount (100-fold in weight) of cytidine, to minimize the probability of
electrons hitting other DNA molecules. The yields of strand breaks per one K-shell
photoabsorption in phosphorus were carefully calculated using the measured yields of ssb
and dsb with photons of on-resonance and o-resonance. The results were unexpectedly
small, 0.2 for ssb and 0.009 for dsb [23]. These values could be compared with the quantum
yield in other photochemical reactions.
In the energy region between 20 eV and 2 keV, the yields of strand breaks in plasmid
DNA were measured at 388, 435, and 573 eV, and it was found that the eciency of strand
breaks per absorbed energy was much less than that in the 2 keV region [24].
It is not easy to compare the yield of strand breaks in the vacuum UV region with
those obtained with x-rays or g-rays, because of the dierence in the dosimetry systems
commonly used. However, when we took the ratio of ssb per dsb, the value is independent
of the dosimetry, and the dierence in the value could be considered as being the result of
dierent mechanisms contributing to the production of dsb. By compiling the data
presented by Hiedas group [12,13,22,25], we could plot the ratio over the whole energy
range from UV to x-ray regions, as shown in Fig. 1. From this gure, they discussed the
following: (1) In the photon energy region around 8 eV, a strand break would be mainly
produced via a superexcited state and dsb could be produced with the least probability by
some mechanism, such as a radical swing over hypothesis (1 dsb over nearly 100 ssb). (2)
Around 20 eV, photoelectrons are emitted from the molecules, which may contribute to
Figure 1 Action spectra for the induction of single strand break (ssb, open circle) and double
strand break (dsb, closed circle) in dry plasmid DNA. Ratio of the cross section of ssb against dsb is
also shown in lower panel. Solid line is reconstructed absorption cross section of the plasmid. (From
Refs. 12, 13, 22, and 25.)
the production of dsb; the contribution of these electrons increases up to the keV region
(1 dsb over 50 ssb). (3) Above 1 keV, the contribution of secondary electrons in the pro-
duction of dsb would become dominant, and the ratio would not increase any further (1 dsb
over 20 ssb). We could say that at least two mechanisms would contribute to producing dsb,
the ratio of the contribution being dependent on the illuminated photon energy.
Biological eects of photoabsorption by exogenous atoms are also interesting be-
cause of a potential application to the radiotherapy of cancer (Photon Activation Ther-
apy). Photoabsorption by the inner shell of a heavy atom has been focused on because of
the large penetration depth of x-rays, and because of the expected large Auger cascade. Le
Sech et al. [26,27] demonstrated that a Pt-containing intercalator, chloroterpyridine
platinum, would act as a photosensitizer when photons corresponding to the absorption
edge of inner shell of Pt are illuminated. They also reported that the ratio of dsb to ssb
increased on on-resonance photoabsorption.
To elucidate the mechanism and the molecular nature of Auger-specic products,
the development of new methods to detect or identify the product at the molecular level
is badly needed. One of the trials to develop a new method was reported by Svensson et
al. [28]. They successfully detected fragments from ATP irradiated with x-rays, or bom-
barded by electrons, the energy of which was tuned to the binding energy of the K-shell
electron of phosphorus, and fragments from cystine bombarded with electron tuned to
the binding energy of sulfur K-shell, using a time-of-ight mass spectrometer. Although
this method is presently applicable only to small molecules of high vaporing pressure, it
would be a powerful method for studying the mechanism to produce molecular damage.
4. EFFECT ON AMINO ACIDS
Using the method mentioned above, the eect of photoabsorption by sulfur atoms in
amino acids was studied by Yokoya et al. [29]. They chose cystathionine as a model mol-
ecule because of the structural advantage that most of the decomposed fragments are
easily detectable amino acids. A comparison of the distribution pattern of fragments
between on-resonance and o-resonance lead to the conclusion that cystathionine was
more frequently cleaved around a sulfur atom than at a bond apart from the sulfur.
5. EFFECT ON WATER MOLECULE
About 70% in weight of living cells is water, and chemical reactions necessary to keep the
cell alive proceed under aqueous circumstances. For this reason, we need to consider the
photochemistry of water when a cell is illuminated with photons of various energies. Very
few data are available so far on the absorption cross section of liquid water. The cross
section starts to increase at around 6.5 eV (190 nm), and grows very rapidly; and the
penetration depth of a photon at 8.3 eV (150 nm) becomes as short as 0.1 Am. A water
molecule, on the absorption of vacuum UV photons, decomposes into H and OH radicals.
For example, these reactive radicals can attack DNA to form lethal or mutagenic damage,
as is well known in radiation biochemistry. Therefore determining the yield of radicals is
very essential to understand the action mechanism of vacuum UV photons on living cells.
Watanabe et al. [30] measured the yield by a Fricke dosimeter, which is commonly used in
g-rays dosimetry. Because of the cuto of the window material (MgF
2
), which can
transmit vacuum UV photons, but is not soluble in water, the obtained values are limited
to less than 8.5 eV. The calculated quantum yield at 8.3 eV (150 nm) was 1.7. For deter-
mining the quantum yield between 6.5 and 7.1 eV, more reliable data on the absorption
cross section are needed. Very recently, Hayashi et al. [31] reported the complete optical
spectrum of liquid water, measured by inelastic x-ray scattering. This method is greatly
expected to solve the above problem.
The Fricke dosimeter is one of the standard systems for the dosimetry of ionizing ra-
diation. Hoshi et al. [32] applied this method for dosimetry of monochromatized
synchrotron x-rays at 8.86 and 13.55 keV. In the soft x-ray region, the Fricke yield was
measured with a photon energy down to 1.8 keV. The yield was found to decrease with a
decrease in the photon energy [33]. The data that they presented was the rst experimental
data in this energy region, which should be compared with the values recommended by
ICRP report No.17 (1970). In this energy region, energetic photoelectrons are produced in
water, most of which are ejected from the K-shell of oxygen because of the largest cross
section. The energy of the electrons is the photon energy minus 0.54 keV (binding energy
of K shell electron of oxygen). Therefore the observed photon energy dependence could be
considered to be a consequence of the dierence in the structure, or distribution, of the
energy deposition events along the electron track, not the nature of a photoabsorbing
atom or molecule. To characterize the structure of energy deposition by a charged particle,
linear energy transfer, or LET, is commonly used. However, for electrons, this parameter
might not be appropriate, because the track of an electron is not as straight as those of
heavy particles. To study the characteristics of low-energy electrons, simulation method
seems to be the only way.
The Fricke solution contains iron ion in its constituent, and one might expect the
eect of inner-shell photoabsorption of iron around the energy region of the Fe K-shell
absorption edge. No photon-energy dependence of the Fricke yield around the K-shell
absorption edge of the ion was found, which was explained by the small abundance of iron
in the sample.
6. EFFECT ON DNA IN SOLUTION
When DNA is illuminated with vacuum UV photons in an aqueous solution, the induced
reactions become more complicated. In the energy region less than 6.5 eV (190 nm) where
water is transparent, the photoabsorbing molecule is DNA itself; but with 7.7 eV (150 nm)
photons, the water molecules absorb almost all photons illuminated onto the sample. In
this transient region, the sensitivity of single strand breaks were measured using plasmid
DNA under dierent buering conditions [34,35]. They found that the peak sensitivity
moves depending on the scavenging condition in the sample, although they conrmed that
the main attacking agents are water radicals produced by the absorption of VUV photons.
They discussed this dependence from the viewpoint of the absorption cross section of the
constituents of the sample solution and from the dierence in the initial distribution of
short-lived OH radicals, depending on the photon energy [36]. The complicated behavior
of the photon energy dependence was recently discussed again by Nikjoo et al. [37].
When aqueous samples are irradiated with soft x-rays, fewer photons are absorbed by the
target atom in the molecule because of the less abundant atoms in the sample. Also, a
greater fraction of the photon energy is taken away by photoelectrons and/or Auger
electrons from the atom in which the photoabsorption event has occurred than in the case
of low-energy VUV photons. For this reason, the eect of specic photoabsorption events,
such as inner-shell photoabsorption followed by Auger cascade, is generally believed to
become less important in the nal consequences. However, studies on DNA or nucleotides
in aqueous solution are absolutely necessary for understanding the eect on living cells,
because living cells contain about 70% of water in total weight.
The rst work was performed by Takakura [38], who irradiated a concentrated so-
lution (200 mg/mL) of bromo-deoxyuridine-monophosphate (Br-dUMP) with monochro-
matic x-rays below (13.43 keV) and above (13.49 keV) the absorption edge of bromine.
Br-dUMP can be incorporated into a living cell instead of dTMP. Radiolytic products,
such as deoxyuridine-monophosphate (dUMP), uracil, and bromo-uracil (Br-uracil), were
quantitatively analyzed using high-performance liquid chromatography (HPLC) as a
function of the absorbed dose in the sample solution. The photon energy dependence
was studied on the yield per absorbed energy. The ratios of the yields of products between
x-rays of 13.49 and 13.43 keV were 2.2 for dUMP, 1.02 for Br-uracil, and 1.23 for uracil.
On the other hand, only a small dierence between x-rays of 13.49 and 13.43 keV was
observed for the yield of uracil released from dUMP irradiated in aqueous solutions. The
energy-dependent enhancement of debromination was considered to be caused by the
inner-shell photoabsorption of bromine, followed by Auger eects. Also, interesting
results were that the yield of debromination per absorbed energy of 100 eV ( G-value)
was 10.5 at 13.49 keV and 4.7 at 13.43 keV. This means one photon induces 13.49/
0.1=134.9 debromination events at 13.49 keV. This suggests that a sort of chain reaction
participates in debromination, and that this reaction is enhanced by the inner-shell
photoabsorption of bromine.
Further work was performed by the same group using an adenosine 5V-triphosphate
(ATP) solution as the sample. They irradiate a concentrated ATP solution (155 mg/mL)
with three energies (2.146, 2.153, and 2.160 keV) of monochromatic soft x-rays around the
absorption edge of phosphorus; the yields of adenine, adenosine 5V-monophosphate
(AMP) and adenosine 5V-diphosphate (ADP) were analyzed with HPLC. The yields of
these three products clearly showed an energy dependence, indicating that the decom-
position of ATP is enhanced by the photoabsorption of phosphorus [39]. The yield of
adenine at the resonance photoabsorption of phosphorus (2.153 keV) was 1.6 per
absorbed energy of 100 eV, indicating that one photoabsorption produces 2.153/
0.1=21.5 adenine molecules. It should be noted that the number of Auger electrons
emitted from phosphorus is smaller than that from the bromine K-shell vacancy. Using
the same sample system, Kobayashi et al. [40] studied the yield of adenine from an ATP
solution with dierent concentrations. The enhancement ratio of the yields, yield at 2.153
keV/yield at 2.146 keV, was found to be concentration dependent. It was considered that
one of the reasons why the eect of inner-shell photoabsorption could be observed in
aqueous solution is the high concentration of the target molecules in the solution, which
increase the atomic abundance in the sample. However, the concentration dependence of
the enhancement cannot be explained. One hypothesis to explain the concentration-
dependent enhancement might be that the inuence of the inner-shell photoabsorption
followed by Auger eect is restricted within a close vicinity of the photoabsorption site.
Strand breaks in plasmid DNA in aqueous solution were also studied by several
groups. Takakura et al. [41] irradiated a plasmid DNA solution (1 mg/mL) with
monochromatic soft x-rays around the K-shell absorption edge of phosphorus. Single
and double strand breaks were analyzed with gel electrophoresis, the same method as that
in the case of a dry sample. They succeeded to observe an enhancement in the yields of ssb
and dsb in plasmid by the resonance photoabsorption of phosphorus, although the photon
energy dependence was not the same. It was surprising that the enhancement was observed
at low concentrations of DNA solution (1 mg/mL), much lower than in the case of Br-
dUMP or ATP. The enhanced induction of ssb and dsb might be explained as follows: The
microscopic density of nucleotides could be considered to be high in the local volume
including DNA and, hence, the concentration-dependent enhancement of the inner-shell
photoabsorption might be observable, as was observed in a concentrated ATP solution.
To investigate the possibility of photon activation therapy, the eect of the inner-
shell photoionization of exogenous atoms on plasmid was studied. Takakura [42] studied
the eect of the inner-shell photoabsorption of calcium, and observed that the mono-
chromatic x-rays tuned to the absorption edge of calcium. Recently, the eect of Pt-
containing chemicals has been studied. An intercalating agent, chloroterpyridine platinum
(PtTC), was mixed with plasmid DNA with a ratio of 1 Pt atom per 10 nucleotides, and
the solution was irradiated with monochromatic X rays tuned to the resonant photo-
absorption energy of the L(III) shell of the platinum atom. Although the atomic
abundance of Pt was very small in the sample, the yield of dsb was higher with an energy
above the absorption edge than below the edge [43]. They discussed the possibility that
energetic electrons generated in the sample lose their energy more densely around the
platinum atoms because of the high electron density of platinum, and hence more water
radicals are produced around platinum that bind to DNA.
The photon energy dependence of ssb and dsb induction over a wide energy range,
between 2.14 and 10 keV, was investigated by Tomita et al. [44]. They found that the yield
of ssb increased with an increase in the photon energy, similar to the Fricke yield, but the
yield of dsb showed an opposite dependence as shown in Fig. 2. These phenomena do not
have any relation with absorption spectrum of the sample, but are related to the energy of
photoelectrons generated from oxygen in water. In other words, from the observed results,
lower-energy electrons produce dsb more eciently, but ssb less eciently. This also
demonstrates again that the induction mechanism of dsb is dierent, at least in part, from
that of ssb. The dierence in the distribution and/or density of energy deposition events
along the electron track is considered to be important, which may cause a local dierence
in the concentration of water radicals.
It is suggested from the results with aqueous samples that local distribution of energy
deposition events would be very important in determining the eciency of a biological eect.
The initial process of radiobiological phenomena could be said to be a dissipation process of
the radiation energy. Soon after being deposited fromphotons or electrons, the local energy
density is very high, and every kind of instability, such as radicals, which can cause
changes in biomolecules, are produced around the site. The reactive species then diuse
away from the deposition site to reach a homogeneous distribution. During early times of
these processes, the distribution of radicals retains the original site where the energy
deposition event took place. For example, the dsb of DNAseems to be more likely produced
at such an early stage of the process, while ssb can be produced even after homogeneity is
attained. Radiation chemistry in the early stage should be promoted more. When we move
on to the circumstances such as inside the cell, where biomolecules are densely and
inhomogeneously dissolved, a more complex reaction system is waiting to be resolved.
7. EFFECT ON BIOLOGICAL CELLS
In this section, studies using living cells and phages in the energy region below 140 nm are
described. The energy dependence observed in most of these studies could be explained by
the transition in the mode of action on DNA by photon, or by the penetration depth of
vacuum UV photons in living systems, especially in living cells containing a large amount
of water. The water molecules work as a shielding layer as well as attacking agents when
they absorb photons. The simplest biological system including DNA would be viruses or
phages. These can survive in a vacuum because they do not contain any liquid water. A
coating layer of protein is so thin that vacuum UV photons can reach DNA and produce
damage, as observed in the case of dry plasmid DNA. Maezawa et al. [45] reported that
the energy dependence of the inactivation of the T1 phage was similar to the spectrum of
DNA. The transition of DNA damage from dimer type to another one was substantiated
Figure 2 Photon energy dependence of the yield of ssb (open circle) and dsb (closed circle) per
absorbed energy in plasmid DNA irradiated in aqueous solution [44]. The Fricke yield is also shown
for comparison (closed triangle).
by the dierence in the susceptibility to the repair ability of a host cell or to the photo-
reactivation treatment. Similar results were obtained using a spore of bacterium, another
small and dry system, by Munakata et al. [46].
When larger systems, such as yeast cells, were used, the penetration depth of vacuum
UV photons into cell nuclei becomes important. Ito et al. [47] found that yeast cells were
killed by vacuum UV as well as UV, but that genetic changes were not induced by vacuum
UV. Vacuum UV was suspected not to produce any DNA damage in yeast cells, because
genetic changes can be considered to be a result of DNA damage. Instead, they found that
damage in the cell membrane was produced. These ndings suggest that vacuum UV
cannot penetrate into cell nuclei and, hence, cannot produce DNA damage, and that cell
death by vacuum UV is attributable to damage in the cell membrane. They pointed out
that the action spectra of inactivation and of membrane damage were similar to the
absorption spectrum of liquid water in vacuum UV region, suggesting that membrane
damage was produced by an attack of the water radicals, the dissociative fragments of
water molecules. These works and related articles have been reviewed by Ito [1].
Living cells consist of various components, such as nucleic acids, proteins and amino
acids, lipids, and water. Because of a large abundance of water, most photoabsorption
events occur at oxygen of water, and nearly monoenergetic electrons (kinetic energy 0.5
keV less than the photon energy). The biological eects of monochromatic photons have
been studied from two points of view: (1) An enhancement of biological eects by inner-
shell photoabsorption, followed by the Auger eect has been investigated in relation to the
possibility of the photon activation therapy of cancers. (2) Rather basic studies on the
electron energy dependence of the radiobiological eect were investigated to understand
the biological eects of high-energy g-rays.
In 1985, preliminary data on the enhanced killing of HeLa cells prelabeled with 5-
bromodeoxyuridine were reported by Shinohara et al. [48]. The enhancement by bromine
inner-shell photoabsorption was intensively studied by Maezawa et al. [49] using E. coli
cells. They clearly observed the enhancement by comparing the eect of monochromatic x-
rays above the absorption edge with those of x-rays below the edge. They also found that
the enhancement was more clearly observed in the presence of dimethylsulfoxide, a radical
scavenger, suggesting less importance of the radical-mediated processes. Similar work was
performed using a mammalian cell line sensitized with 5-bromodeoxyuridine [50] or with
5-iododeoxyuridine [51]. Usami et al. [52] discussed the enhancement by bromine incor-
poration into DNA from the view point of the absorbed energy, or dose, using the substi-
tuted fraction of thymine with bromo-uracil, and concluded that the enhancement could
not be solely explained by the increased absorbed energy, or dose, and that some damage
specic to the Auger cascade might be produced. Jonsson et al. [53] tried to nd the
enhancement by inner-shell ionized indium atoms incorporated into the cell. No signicant
dierence in survival between irradiations above and below the K-edge could be observed,
because of the small amount of indium incorporated into the cell. This demonstrates the
importance of selecting the chemicals or methods to deliver the target atoms into the cell,
when photon activation therapy becomes eective.
The eect of phosphorus photoabsorption in DNA has been intensively inves-
tigated because the discovery of the resonance absorption at the K-shell absorption edge
(Fig. 3). Soon after the discovery of large resonance photoabsorption in the K-shell edge
(2.15 keV) of phosphorus in DNA, Kobayashi et al. [18] studied the biological eect of
phosphorus photoabsorption in yeast cells. They found that the photon energy depen-
dence of the killing eect and of the induction of genetic changes were very similar to
the resonance absorption spectrum of DNA (Fig. 4). On the other hand, they could not
detect any impairment of the cell membrane consisting of a bilayer of phospholipids.
These results clearly indicate that soft x-ray photoabsorption by phosphorus produces
DNA damage, which causes biological eects, such as cell killing and the induction of
genetic changes. For the case of induction of genetic changes, they calculated the quan-
tum eciency of induction to be 0.13, assuming the target size to be the size of the gene
concerned.
The enhancement of biological eects by inner-shell photoabsorption in DNA could
be considered to be caused either by the increase in the amount of energy deposited locally
around the photoabsorption site, namely DNA, or by the production of DNA damage
specic to inner-shell photoabsorption, which could be repaired less by the cellular repair
system. The former possibility can only be discussed from a theoretical nanodosimetric
point of view. Experimentally, the latter hypothesis has been challenged by radiobiologists
using repair-decient strains. The most probable candidate of nonrepairable damage has
been considered to be a complex damage composed of more than one dsb, or dsb and
other types of damages, produced very near each other. This type of damage is called
clustered damage, and is now being intensively studied by many radiobiologists and
biochemists.
Watanabe at al. [54] compared the induction eciencies of various biological
endpoints using Syrian golden hamster embryo (SHE) cells. They found that monochro-
matic soft x-rays tuned to the resonance absorption of phosphorus (2.153 keV) were more
Figure 3 Absorption spectrum of the DNA lm around the K-shell absorption edge of phos-
phorus [18]. Dotted line is the total photoelectron yield of KH
2
PO
4
. Three vertical arrows indicate
the X-ray energies used for the irradiation experiments shown in Fig. 4.
ecient in the induction of mutations and chromatid aberrations than o-peak x-rays
(2.147 and 2.159 keV). When compared at equal survival levels, there was no dierence in
the frequencies of mutations and chromatid aberrations in cells irradiated with soft x-rays.
On the other hand, a morphological transformation was more eciently induced with
2.147-keV x-rays than with 2.153- and 2.159-keV x-rays. To see the nature of DNA
damage produced by inner-shell photoabsorption, studies using repair-decient stains
were made. Maezawa et al. [55] compared the enhancement by phosphorus photo-
Figure 4 (a) Lethal eect and (b) induction of genetic changes in yeast cells irradiated with x-rays
tuned to resonance absorption peak [2.153 keV (triangle)] and both sides of the peak [2.147 eV
(square) and 2.160 keV (circle)]. (From Ref. 18.)
absorption between wild type and several repair-decient strains of E. coli. The enhance-
ment ratios, dened as the ratio of the killing sensitivity of 2.153 keV to that at 2.146 keV,
were 1.32 for the wild type, repair-procient strain, and 1.42 to 1.54 for repair-decient
strains. They also calculated the number of lethal hits per Auger cascade for the strains
examined. The value for the recombination-decient strain was highest (0.65), while the
value for the wild strain was 0.11. This suggests that most of the DNA damage produced
by the Auger cascade would be double strand breaks, which can be repaired by the
recombinational repair pathway, and that some part of the damage produced by Auger
cascades was repaired in wild-type strains. Usami et al. [56] investigated the enhancement
by phosphorus photoabsorption using a repair-decient strain of yeast, which cannot
repair double strand breaks of DNA. Double strand breaks were expected to be more
eciently induced by phosphorus photoabsorption. They found that the enhancement
disappeared in the repair-decient strain. On the other hand, when wild-type cells were
given more time for repair, the enhancement became larger than in the reference condition.
These results were explained as meaning that the fraction of nonrepairable dsb produced
by inner-shell photoabsorption was too small to be detected in the cell-killing eect where
the damage was not repaired at all, while the fraction of nonrepairable damage became
larger after dsb repair had fully operated compared to before. Seemingly, nonrepairable
damage is concentrated by the repair system of the cell. The dierence in the enhancement
in repair-decient strains between E. coli and yeast might be because of the dierence in
the DNA damage repair system of each species.
The repair of damage produced by phosphorus photoabsorption was more directly
investigated by Maezawa et al. [57]. They measured chromatin breaks of cells irradiated
with x-rays of on- and o-peak the resonance absorption of phosphorus using the
premature chromosome condensation (PCC) method. It was found that chromosomal
damage produced with 2.147-keV x-rays was repaired to one-third by the action of the
cellular repair system, while the damage by on-peak x-rays (2.153 keV) was not repaired at
all. The elucidation of the mechanism by which DNA damage leads to chromosomal
damage might help us understand the chemical nature of Auger-specic damage.
These lines of results using repair-decient strains suggest that inner-shell photo-
absorption, followed by the Auger eect, more eciently produces a nonrepairable type of
damage than x-rays with other energies. However, studies to nd or identify these types of
damages at the molecular level have not yet been successful so far.
Another type of research using monochromatic x-rays is to investigate the electron
energy dependence of biological eects. In living cells containing a large amount of
water, most of the photoabsorption events of low-energy x-rays occur at the oxygen
atom of water, which generate monoenergetic photoelectrons in the sample. The induc-
tion of chromosome aberrations was studied in human peripheral blood lymphocytes
irradiated by monochromatic soft x-rays of quantum energy in a range between 4.8 and
14.6 keV [58]. These x-rays were found to be more eective in producing chromosome
aberrations (dicentrics and rings) than
60
Co g-rays. The observed dependence of the
eciency on the LET of the photoelectrons and their associated Auger electrons was
discussed in relation to the dual nature of chromosome aberration formation. The lethal
eect of ultrasoft x-rays was investigated using Chinese hamster V79 and mouse C3H
10T1/2 cells [59]. They chose 273- and 860-eV ultrasoft x-rays, both of which have the
same attenuation depth into the cells. Such an isoattenuating energy pair allows a direct
examination of biological eectiveness of ultrasoft x-rays. They could not nd any
signicant dierence in the lethal action of these x-rays. These results should be discussed
from the viewpoint of the energy distribution of the generated photoelectrons and Auger
electrons in the sample.
The photon energy dependence of inactivation and mutagenesis in the whole energy
region between 0.1 and 300 nm was investigated by Munakata et al. [46,60,61] using
Bacillus subtilis spores. Spores can survive in a high vacuum, in which vacuum UV and
ultrasoft x-ray photons can be exposed on samples. Also, its size is small enough for
vacuum UV photons to penetrate into and reach DNA. They constructed the photon
energy dependence of inactivation and mutagenesis [62]. Some of the characteristics that
they found are:
(1) Shift in the nature of DNA damage that occurred between 5.6 eV (220 nm) and
8.3 eV (150 nm). This shift is considered to be a shift from the base dimer-type
damage to the strand-break type, which could be expected with work using DNA
molecules.
(2) A decrease in the biological eciency was observed in the vacuum UV region
because of the shielding eect of the outer materials in a spore.
(3) In the soft x-ray region, an enhancement by the photoabsorption of phospho-
rus and of calcium was observed. The condensation of calcium near DNA in
spores, as a form of dipicolinic acid, has already been reported [63]. The cal-
cium atom has acted in the same manner as exogenous sensitizers.
8. FUTURE PERSPECTIVE
Data on the photon energy dependence of the biological eect has been accumulated fairly
well with strand-break induction in plasmid DNA, and with an inactivation of the spore of
a bacterium. These studies gave us many clues to understand the induction mechanism of
biological eects in cells. However, for a complete understanding, research in the following
areas should be highly promoted.
(1) The spectroscopy of biomolecules, themselves alone, and in complexes with
water molecules over the whole energy region from vacuum UV to x-rays.
(2) Photochemistry and radiation chemistry of biomolecules in vacuo and in water.
Radiolytic products from Auger cascade are interesting from the viewpoint of
radiotherapy. The development of irradiation systems is required in which liquid
samples can be irradiated with vacuum UV or ultrasoft x-rays of high intensity.
(3) From the viewpoint of the electron energy dependence of biological eects, the
eciency of low-energy x-rays on living cells should be studied. Because the
electron track is composed of a track segment of dierent energy, data over a
wide energy range are necessary.
(4) The development of new methods for studying the photon-induced decom-
position, or damages, of biomolecules and for studying radical reactions in the
early stage in water.
ACKNOWLEDGMENTS
The author expresses sincere gratitude to Prof. K. Hieda for the critical reading of this
manuscript. Thanks are also due to Dr. N. Usami for her help in preparing the manuscript.
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17
Track Structure Studies of Biological Systems
Hooshang Nikjoo
Medical Research Council, Harwell, Oxfordshire, England
Shuzo Uehara
Kyushu University, Fukuoka, Japan
1. INTRODUCTION
Although radiation biology over the past decade has made striking progress in under-
standing the components of radiation damage in the cell, the future direction is in under-
standing the biological systems, using theory, computation, and simulations as an integral
part of experimental method. Useful biophysical models give predictions that can be related
to other biological phenomena and are not just simulations of experimental data and
observation. An immediate question comes to mind, whether there is a role for mathematics
in biology and cancer research. Unlike in more pure sciences such as physics, most biological
work is highly descriptive and entities are complex and not easily expressed as a set of
invariant quantities. Despite such diculties, over the past half century, there has been a
rapid surge in mathematical theories along with the advances in laboratory and clinical
cancer research to provide generalized description, e.g., observations on population and
dynamics in tumor growth, diusion processes, protein regulations, and the role of kinase
pathways in human diseases and others in genetics and ecology. To obtain an insight into the
mechanismof radiation oncogenesis especially at lowdoses relevant to radiation protection,
it is necessary to formulate a radiation risk model that attempts to relate the early molecular
damage to the observed eects. Such an attempt requires a quantitative description of the
general features of radiation insult in terms of DNA damage as a starting platform to in-
vestigate the role of repair and cell survival using more exact mathematical expressions.
Although such a goal is yet a long way o, this chapter shares with the reader some aspects of
knowledge and experience gained in description and quantication of the spectrum of DNA
damage and deeper understanding of the nature of radiation insult.
A current concern in radiation biology is understanding the mechanism of damage to
cells and tissue and quantication of the health hazards of ionizing radiation of dierent
qualities, and in particular quantication of human cancer risks at low doses and dose rates
to the general population [1], and specic group of workers such as space-radiation expo-
sures to astronauts [2]. This concern is evident from major scientic programs currently in
progress in Europe [3] and the United States [48].
In the recent past, our perceived understanding of DNA as the target for ionizing
radiation has become more complex with discoveries of new phenomena such as the by-
stander eect [9], the adaptive response [10], and the genetic instability [11,12]. These new
phenomena have shed doubt on the estimation of cancer risk solely by extrapolation of dose
response from high to low dose and dose rates [13,14]. With recent accelerated progress in
molecular biology techniques and advances in theoretical methods, attention has become
more focused on mechanistic studies of eects of ionizing radiation. To this end, track
structure has provided a theoretical/simulation framework to investigate those parameters
of ionizing radiation that predominantly determine the nature and magnitude of the nal
eect [15,16] (see also Chap. 4]. In general, microdosimetry and track structure have
tried to scrutinize and understand aspects of radiation damage in cellular structures from a
theoretical approach based on fundamental physical and chemical principles and provide
hypotheses that are experimentally testable. In particular, track structure provides a basis
for understanding the underlying mechanismthat shapes the doseeect relationship. There
is a wealth of information and data accumulated on harmful eects of radiation track that
needs to be placed in the framework of a general descriptive theory. For example, there are
considerable data: on the early eects of radiation damage on DNA [17]; on chromosome
aberration [1821], mutational events [22,23], and genetic instability [11]; on early clonal
expansion of the cell to neoplasia and on the nal expression of malignancy [24]. This
chapter includes a brief description of application of track structure in model calculations of
DNA damage, application of DNA damage in radioprobing of novel DNA structures,
bystander eect, and latest progress in track simulation. The model calculations presented
here are a testimony to the depth and breadth of track structure calculations that have been
applied in a broad range of subjects.
2. TIME SCALE
Biological responses to ionizing radiation, broadly speaking, depending on the end point,
can be divided into early and late eects. Early eects are those that become apparent within
milliseconds to days following irradiation. Late eects manifest themselves within weeks to
years following exposure. Radiation injury begins with the physical processes of energy
deposition in the medium, at times less than femtoseconds, leading to ionizations and exci-
tations. The initial physical processes lead to molecular damage by direct interaction of the
radiation with the target and through the generation of free radicals, oxidizing agents and
other molecular species, and the bystander signals. Molecular damage is usually expressed
through alteration of biochemical processes and is amplied by biological mediators. In
addition, damage may persist, which is not generally visible or clinically detectable, leading
to genetic instability. Damage can also indirectly arise from signals received from the neigh-
boring hit cells. In both direct and indirect modes, we assume DNA is the primary target
leading to observed cellular eects. Fig. 1 shows a owchart of such ideas including the
DNA repair pathways and other processes leading to cell inactivation and cancer.
The sequence of events starting with the transfer of energy from the primary particle
to the molecules of the medium initiates a chain of events depending on the magnitude of
energy being transferred and electronic structure of the material of the medium. These
interactions, in the form of clusters of ionizations and excitations, set in motion one or
more electrons in the surrounding molecules. These events have a random distribution and
normally no two particles produce the same distribution. The energy degradation of the
primary particle continues by successive interactions with the neighboring molecules and
the ejection of secondary electrons until its excess energy is completely lost and the electron
becomes trapped by the electrostatic charges. The trapped electron is usually referred to as
the hydrated electron (e
aq
), which behaves as a free radical, diuses, and interacts with other
atoms until captured. The creation of hydrated electrons is regarded as the start of the
chemical stage at which time the systemis in thermal equilibrium(10
12
sec and <0.025 eV).
A simple consequence of free radical diusion and reactions with other molecules is the
modication and amplication of existing molecular damage from the physical stage as the
consequence of direct interactions in the target site.
Chemical alterations due to direct ionization of the molecules and free radical reac-
tions lead to degradation of the biomolecule and induction of cross-linking, and intercross-
linking of the DNA and proteins [25]. These and other changes to the conformation of the
biomolecules may change the enzymatic activity of the cell [26]. Table 1 provides a quan-
titative summary of the number of events produced by 1 Gy of radiation of dierent quality
in a mammalian cell. The dierences observed in biological eects of radiations of dierent
quality may arise not only fromdierences in their track structures but also from dierences
in physical and physiological conditions. It is noted that although energy deposited in the
cell by 1 Gy of radiation produces a large number of events, only a fraction of this leads to
induction of molecular damage. In mammalian cells, the majority of single-strand breaks
(SSB), in the form of single nucleotide gaps, and damage to DNA bases, in the form of base
products, are readily repaired [27]. Although the frequencies of observed changes in a single
cell induced by ionizing radiations are very low, it is widely believed that most cancers arise
Figure 1 Schematic sequence of events following DNA damage.
from multiple changes in a single cell, in which at least one of the initial events could have
been induced by radiation in the damaged cell or its progeny [28].
3. SIZE SCALE
3.1. Model of DNA
Dimensions of the DNA and its higher-order molecular structures, the nucleosome and the
basic ber, are given in Table 2. It is assumed that the genome of the mammalian cell con-
Table 1 Average Yield of Damage in a Single Mammalian Cell after 1 Gy of Radiation
Radiation Low-LET High-LET Comments
Tracks in nucleus 1,000 4 100 keV electrons and
3.2 MeV a
a
Ionizations in nucleus 100,000 810
5
100 keV electrons and
3.2 MeV a
b
Excitations in nucleus 100,000 810
5
100 keV electrons and
3.2 MeV a
b
Base damage (BD): SSB 3.3 3.4 100 keV electrons and
3.2 MeV a
c
8-Hydroxyadenine 700 [222]
Thymine damage 250 [222]
DSB: initial 38 46 3.4 MeV a [56]
DNA protein cross link 150 [222]
Chromosome aberration 1 3 [220]
Dicentric per cell 0.1 0.4 [220]
HPRT mutation 6.910
6
8.310
5
[219]
HPRT mutation (BG) 3.210
6
310
5
[219]
Lethal lesions 0.5 2.6 [221]
Lethal lesions per DSB 0.01 0.045 250 KV X, 100 keV/Am a [221]
DSB per lethal lesion 87 22 250 KV X, 100 keV/Am a [221]
Cell inactivation 30% 85% [223,224]
Complex SSB 4% 30% 100 keV electrons,
3.2 MeV a [7981]
Complex SSB
B
40% 70% 100 keV electrons,
3.2 MeV a [7981]
Complex DSB 20% 70% 100 keV electrons,
3.2 MeV a [7981]
Complex DAB
B
60% 90% 100 keV electrons,
3.2 MeV a [7981]
Fract hybrid DSB 0.38 0.25 100 keV electrons,
3.2 MeV a [7981]
d
a
Data from authors Monte Carlo track structure calculations.
b
For a nucleus 10-Am diameter.
c
See Table 5.
d
Hybrid DSB: when a SSB induced by direct energy deposition converted to a DSB by OH.
tains 6 pg of DNA in a nucleus, a physical size of 6349 Mbp [29], a molecular weight of an
average base pair of 660, and a length of a base pair of about 0.34 nm.
Models of DNAof various degrees of sophistication have been used in the calculations
of radiation-induced DNA damage. These can be classied into three groups. The simplest
of DNA models is a linear segment in the form of a cylinder [30]. These segments can be
generated along random chords cutting a convex body (spherical nucleus) using the method
of A-randomness [31]. This model has mainly been used to obtain frequencies of energy
depositions in macromolecular structures without a priori assumption of the role of the
atomic structure in determining the biological responses. A more realistic model used in our
early studies of DNA damage is the volume model of DNA [32]. In the volume model, DNA
is in its native B-formwith a diameter of 2.3 nmand divided into 0.34-nmslices. In turn, each
slice is divided into three volumes comprising the central core representing the volumes of
the complementary paired nucleobases and the two arches, each representing the volumes
occupied by the deoxyribosophosphate backbone of each strand. This model does not take
into account the detailed atomic structure of DNA. The third category is the sophisticated
atomic models of DNA that have been available for a number of years, and can now readily
be generated using commercially available programs such as Newhelix [33], Curves, and
MidasPlus [34,35]. Further renements of the latter models include the distribution of sol-
vent molecules around the sugarphosphate backbone and the nucleobases [36 37]. Mod-
eling of higher-order structures of DNA, nucleosome, chromatin, and other forms such
as triplexes, have been made by several authors [3841] and also available from the PDB
library.
3.2. A Model of the First Hydration Shell of DNA
The following describes the development of an atomistic model of DNA including the rst
hydration shell of a B-DNA [37]. Water plays an important role in the three-dimensional
structure of DNA, the conformation it adopts, and its response to radiation. Inuence on
the conformation of DNA by the solvent has been known since the earliest ber diraction
studies [42]. The native conformation of the macromolecule to a large degree is inuenced by
inter- and intramolecular forces, such as hydrogen bonding forces, repulsive and dispersive
forces, and interaction with the solvent. At high relative humidity or water activity, cor-
responding to low salt or low atomic organic solvent content, DNA adopts the B-form,
which is considered to be the most biologically relevant form of DNA. If the relative hu-
midity is lowered, DNA transforms from B-form to A-form.
Table 2
Structure
Diameter
(nm)
Segment
Length (nm)
Number per
Genome Comment
DNA segment 2.3 2.3 9.310
8
Assuming 6 pg of DNA in
nucleus, MW of 660, DNA
duplex 1.86-m length
Nucleosome 10 5 single
nucleosome
2.910
7
190 bp containing 50 nm of
DNA including the linker
Chromatin
segment
30 30 1.910
6
Solenoid of nucleosomes
The basic building block of DNA is the nucleotide. The backbones run in opposite
directions with each base pair having a purine base (A/G) hydrogen bonded to a pyrimidine
base (T/C). The purine and pyrimidine bases are on the inside of the helix while the phos-
phate and sugar are on the outside. The two chains are held together by hydrogen bonds
between the base pairs. Adenine is paired to thymine by means of two hydrogen bonds while
guanine is paired to cytosine by three hydrogen bonds. A single nucleotide consists of three
chemical parts; a simple sugar molecule, an inorganic phosphate and a nitrogen-containing
base. Successive nucleotides are linked together via a phosphodiester bond between the
sugar and phosphate of adjacent nucleotides. The nitrogen-containing bases are not in-
volved in any covalent linkages other than their attachment to the sugarphosphate back-
bone. It is the sequence of these nitrogen-containing bases along the sugarphosphate
backbone that constitutes the unique structural and functional individuality of the DNA
molecule. The nitrogen bases are linked at the C
1
position while the C
2
and C
4
hydroxyl
groups participate in phosphodiester bonds. The nitrogen-containing bases are either the
double-ringed purines or the single-ring pyrimidines. The phosphate group is present as part
of a diester linkage. The DNA bers can exist in three major forms, as B-DNA under
conditions of high humidity, as A-DNA, and a left-handed family of Z-DNA. The dier-
ences between the families occur in the way the sugarphosphate backbone is wrapped
around the helix axis, the way in which the base pairs are stacked and in the pucker of the
furanose ring [43]. The A-DNA form with 11 base pairs per pitch of 28 A
is much more
compressed than the B-DNA form with 10 base pairs per pitch of 34 A
. Another dierence
between the A and B forms is that the sugar in the B-DNA is puckered in the C(2V)-endo
family region, extending from O(4V)-endo to C(1V)-exo, resulting in a wide interphosphate
separation of 6.6 A
along the chain. For the A-DNA, the sugar puckering is conned to the
C(3V)-endo resulting in a shorter interphosphate separation of approximately 6 A
. Thus
phosphate groups in A-DNA can be bridged by water molecules as the interphosphate
distances is not too large while all phosphate groups are individually hydrated because the
interphosphate separation is too large [44]. These dierences results in dierent hydration
patterns around the phosphate groups, which may oer a scheme for the transition from A-
to B-DNA. At lower humidity, the hydration becomes more economical and the sugar
puckering changes, eectively reducing the interphosphate separation and so allowing water
molecules to bridge the free phosphate oxygen atom [45].
DNA hydration studies with various techniques have shown that there are approx-
imately 10 and 20 water molecules in the rst hydration of A- and B-DNA, respectively.
These water molecules bind in decreasing order of strength to the anionic oxygens of the
phosphate group, to the ester oxygens of the phosphodiester linkage, to the O(4V) oxygen
of the furanose ring, and to the electronegative atoms of the base pairs [46].
Distribution of water molecules around the polar atoms of a decamer canonical
B-DNA structure were obtained from quantitative analysis of the solvent interactions
within hydrogen bonding distances of polar atoms of oligonucleotides using 12 B-DNA
oligonucleotide crystal structures [37]. Table 3 shows the distribution of water molecules
around the bases, the phosphate group, and the sugar. The data are presented in terms of
polar coordinates around a polar atom in the plane of abc as indicated in the table. Data
shows that water interactions around the bases mainly occur with the polar atoms of the
major and minor grooves. In this manner, the data in Table 3 have been used to generate
variable DNA segments. The rst atom in the table given in bold type is the atom at the
origin of the r, #, U coordinate system.*
*Atomic coordinates of the hydrated B-DNA can be obtained from the author.
4. APPLICATION OF TRACK-STRUCTURE CALCULATIONS
IN UNDERSTANDING RADIOBIOLOGICAL MECHANISMS
Motivation for understanding mechanism of cellular damage by ionizing radiation tracks
dates back to the pioneering work of Lea [47]. Investigators since then have tried to relate
the initial events produced when a track of ionizing radiation traverses the cell nucleus to
the observed biological lesions. In most cases, such a description starts with knowledge of
spatial distribution of energy loss in subcellular structures such as DNA. For example, for
practical reasons, assessment of risk of radiation exposure requires allowances to be made
for the dierences in biological eectiveness of dierent types of radiation. Because of the
stochastic nature of radiation, such assessments depend on the absorbed dose in the vol-
ume of the target, the quality of radiation, and the size of the target. We also know that
relevant biological eects of radiation are mostly because of damage in individual cells. To
this end, it has also been established that the spatial and temporal distribution of radiation
interactions within the cell or its nucleus has an important inuence on its biological
eectiveness. Therefore these distributions must be considered if we are seeking either
practical quantities for comparison of dierent radiations in risk assessment and therapy,
or seeking a greater understanding of the fundamental problems in the mechanism of ra-
diation action. In pursuit of a suitable description of the mechanism(s) of radiation eects,
a number of biophysical models have been put forward including the exchange theory
of Revel, the breakage rst theory of Lea and the lesionnonlesion interaction by
Chadwick and Leenhouts [20,48,49,82].
4.1. Energy Depositions in Molecular Targets
Although local energy depositions can be experimentally measured over subcellular dis-
tances of nearly 1-Amdiameter, biophysical theories require knowledge of energy deposition
Table 3 Distribution of Water Sites for B-DNA
Atom
abc r(A) hj /j
Phosphate O1PPO2P 2.91 53 145
2.63 32 103
O2PPO1P 2.95 48 179
2.76 46 74
Sugar O4VC1VC2V 2.84 53 174
Cytosine O2C2N3 2.94 22 160
N4C4C5 3.07 63 9
Thymine O2C2N3 2.77 22 123
2.84 47 104
O4C4C5 2.68 45 15
Adenine N3C4C9 2.84 43 23
N6C6N1 3.18 41 176
N7C5C6 2.70 43 7
Guanine N2C2N3 3.36 24 35
O6C6N1 2.70 43 176
N3C4N9 2.91 45 7
N7C5C6 2.77 46 9
in small targets of the dimensions of DNA molecules. To this end, Monte Carlo track
structure methods allow calculations of energy depositions and DNA damage at resolu-
tions down to subnanometer dimensions (see, e.g., Chap. 4). To obtain the distribution
of energy deposition in molecular targets, the conceptual framework of the method is to
place the track in a virtual volume big enough to contain the entire track and then randomly
place the target structure in the volume. The method ensures the establishment of an elec-
tronic equilibrium and accurate calculation of absorbed dose in the target. In this way,
the energy deposited in the target can be grouped together in slices of 0.1-nm length to give
the total energy in the target. Fig. 2 shows examples of such distributions in three vol-
umes pertaining to a segment of DNA, a nucleosome, and a chromatin ber segment for
dierent radiation qualities. The left ordinate shows comparison of distributions of abso-
lute frequency of energy depositions in the target, randomly positioned and oriented in
water and irradiated with 1 Gy of the given radiation. The right ordinate gives the corre-
sponding average number of events in the target volume in one typical mammalian cell.
Subsequently, more complex forms of DNA structures could be used to obtain more de-
tailed physical and chemical information on the nature of damage from the distributions of
energy depositions.
4.2. Summary
Frequency of energy deposition in volumes of dimensions similar to DNA and other bio-
logical molecules provides a method of interpretation of mechanism of radiation eects. In
this method, the assumption is that radiation quality eects are mostly because of the spatial
properties of the radiation on a microscopic scale. The database of absolute frequencies of
energy depositions in cylindrical targets of dimensions 1100 nm include:
Electrons10 eV to 100 keV [50].
Ultrasoft x-rays (C, Al, Ti, and Cu) [51].
Alpha particles and protons 0.34 MeV/u (track segments) [52].
Protons 1-26 keV (full-slowing-down-tracks) [53].
Alpha particles 2 keV-1 MeV (full-slowing-down-tracks) [54].

Table 4 provides a summary of selected particles, energies, and microdosimetric pa-
rameters available from the monographs. All data are taken from Refs. 5055. In Table 4,
f(>0) is the probability of hit of any size = z
F
1
, z
F
, and z
D
are the frequency- and dose-
averaged mean-specic energies.
Figure 2 Frequency distributions of energy deposition in a target corresponding approximately in
size to a segment of DNA (2.3-nm diameter, 4.6-nm length), a nucleosome (10-nm diameter 5-nm
width), and a segment of chromatin ber (30 30 nm), in water irradiated with soft x-ray, protons,
and alpha particles. The left ordinate gives the absolute frequency f( >E) of deposition events
greater than the energy E (eV) in the target volume when randomly placed in water uniformly
irradiated with 1 Gy of the given radiation. The right ordinate is the corresponding average number
of events in such targets in a typical mammalian cell, using the factors in Table 2. The frequency of
hits of any size is given by f(>0) = 1/z
F
and the number of events, corresponding to the frequency
f(>E), is obtained from N = [ f(>E)/f(>0)]M, where M is the total number of hits.
5. MODELING AND CALCULATIONS OF DNA DAMAGE
Two recent papers provide comprehensive summaries and references to the experimental
data of double strand breaks (DSB) [56,57]. Experimental data of DSB in mammalian cells
using PFGE shows that for a given radiation dose, the relative biological eectiveness of all
radiations is nearly unity [58,59,152]. Such observation begs to ask some questions including
the following: Is cell sensitivity to radiation damage due to biological processing of initial
damage? Is the initial critical damage the same for both high and low linear energy transfer
(LET) radiations? Do biological eectiveness of radiations correlate with dierences in track
structure of high- and low-LET radiations? Do biological dierences correlate with tem-
poral dierences of radiations? Is there a correlation between the cell survival and the num-
zber of double strand breaks? Is there a correlation between the cell survival (or other end
points such as aberration, mutation, and transformation) and the quality of double strand
breaks? Is the eectiveness of low doses of radiation predominantly determined by the local
microscopic features of individual tracks?
Not all the question can be categorically answered. However, our understanding has
been increased from insights oered by modeling and simulation work. In general, it is be-
lieved that there exists a general correlation between the nature of the initial physical fea-
Table 4 Summary of Microdosimetry Parameters
Particle Energy LET (keV/Am) z
F
(kGy) z
D
(kGy)
Electron 1 keV 8.300e+02 1.500e+03
Electron 100 keV 6.300e+02 1.310e+03
Proton 1 keV 8.97 3.255e+02 8.071e+02
Proton 4 keV 25.75 4.309e+02 1.007e+03
Proton 10 keV 53.19 5.934e+02 1.322e+03
Proton 20 keV 79.56 7.496e+02 1.605e+03
Proton 26 keV 91.20 8.016e+02 1.714e+03
Proton 300 keV 58.90 1.014e+03 cGy
Proton 500 keV 40.10 8.596e+02 cGy
Proton 1 MeV 25.80 7.518e+02 1.580e+03
Proton 2 MeV 16.00 7.063e+02 1.390e+03
Proton 4 MeV 8.8 6.528e+02 1.300e+03
Proton 200 MeV 0.45 1.100e+02 1.100e+03
Deutron 0.79 MeV/amu 30.656 8.107e+02 1.476e+03
4
He 2 keV 5.615e+02 1.191e+03
4
He 10 keV 39.52 1.064e+03 1.981e+03
4
He 100 keV 125.94 1.575e+03 3.478e+03
4
He 200 keV 176.57 1.655e+03 3.983e+03
4
He 1 MeV 1.690e+03 4.719e+03
4
He 2 MeV 167.2 1.356e+03
4
He 4 MeV 103 1.090e+03 2.260e+03
4
He 8 MeV 61.4 9.300e+02 1.800e+03
4
He 16 MeV 40.3 7.800e+02 1.550e+03
4
He 20 MeV 32.2 7.200e+02 1.480e+03
4
He 8.89 MeV/amu 21.5 6.925e+02 1.223e+03
C
x
278 eV 1.053e+03
A1
x
1487 eV 9.067e+02
Ti
x
4509 eV 7.168e+02
tures of the track and the possible nal biological lesions [60]; it is believed that damage of
DNA is a key step in the sequence of events that leads to, e.g., radiation-induced cell death
[6165]; it is now widely believed that the initiating events are mostly because of DNA
double strand breaks [66]; it is believed that critical initial damages are mainly produced by
localized clusters of DNA damage [67,28]; and it is believed, in general, that a linear re-
lationship exists between dose and number of DSB, indicating double strand breaks are
formed as the result of a single track interaction [68].
Two approaches to modeling and calculation of strand breaks in general and yield of
double strand breaks in particular have been used. One method is tting various phenom-
enological parameters for particle tracks or energy depositions to measured double strand
breaks data [6971], and the other is the application of mechanistic models to cellular DNA
damage. Application of mechanistic models has become a reality through the advances in
particle track simulation [60,7274], availability of fast computers, and realistic models of
DNA in simple and sophisticated forms. These mechanistic biophysical descriptions have
progressed from considerations of direct eects of radiation alone [30], and contribution of
radical species [7579] in the environment of the cell nucleus to cause DNA damage, in the
form of single strand breaks, double strand breaks, base damage, and complex combina-
tions within the cluster of damage [80 81], to include cellular processes such as DNA repair
[82] and its consequences [83,84].
5.1. Classification of DNA Damage
Two alternative classication schemes have been used for DNA breaks (Fig. 3) [79]. The
scheme considers damage in DNA as: (A) patterns of breaks according to the complexity of
damage (single, double, and their major combinations) on one or both strands and in (B) the
damage has been classied according to the origin of the breaks either from direct energy
deposition or reactions of OH radicals. In these calculations, it is assumed that the yield of
damage from other radical species is negligible. The top and bottom lines represent a two-
dimensional projection of the double-helix sugarphosphate backbone and the two middle
dashed lines represent the individual bases. Vertically, the two center dashes and the cor-
responding sugarphosphates on the top and bottom strands form a two-dimensional pro-
jection of a nucleotide base pair. The maximum distance between two single strand breaks
on complementary strands that are classed as producing a double strand break was set at 10
base pairs [85].
5.2. Parameters of DNA Damage Modeling
In jump-the-detail method, two principle parameters need to be considered. The rst one
is the quantity of energy, or the threshold energy, required to induce a DNAstrand break. A
major problem in quantication of energy required for induction of a single strand break
arises from variability of the total yield of strand breaks in dierent cell lines under dierent
conditions, with dierent types of radiations, and measured with dierent techniques [56,
57]. However, measurements of single strand breaks that are more relevant to the energetic
of DNA damage are less available. Experimentally, such measurements are much more
demanding and where these exist, such measurements have been carried out under dissimilar
conditions unsuitable for comparisons [56,86]. In general, although experimental yield of
strand breaks provide a reliable test for modeling, they do not provide a means to derive
accurate and quantitative values of parameters needed in biophysical modeling. For the
purposes of modeling, we seek information from experiments under controlled conditions
with a resolution of a single base pair. Experiments with the latter criteria can mainly be
Figure 3 Various possible types of damage in the sugarphosphate of the DNA induced by direct
energy deposition or by diusing hydroxyl radicals. Only one type of damage is assigned to each
DNA segment. On the left, DNA damage is shown by an . Combination of one, two, three, or
greater than three single strand breaks on the same strand or on opposite strands have been assigned
as SSB, SSB+, 2SSB, DSB, DSB+, and DSB+. The seven modes of strand breaks can also be
combined with base damages on one or both base moieties (diagrams not shown). The model on the
right-hand side explicitly show the origin of the strand break whether arising from a direct energy
deposition D or from an OH radical I.
found among those using cells labeled with a suitable radionuclide, such as Auger emitting
125
I, rather than external radiations [88,89].
In modeling of DNA damage, various authors have adopted a number of simplifying
and convenient assumptions. These assumptions allow jump-the-details of a full-scale mo-
lecular analysis of the formation of strand breaks by a particle track. Such detailed analysis
at the level of genome is beyond the capability of present theoretical chemistry and molec-
ular dynamic systems [90]. The simplifying assumptions in jump-the-detail include using
probabilities associated with the induction of single and double strand breaks by direct
energy depositions and the reaction of hydroxyl radicals with the nucleobases. Estimation of
energy required for induction of single strand breaks, by direct energy depositions, could
be divided into three categories: those calculations dealing with the stochastic of energy
deposition in the volume of DNA [68]; calculations using physical parameters such as oscil-
lator strength of the target (e.g., DNA) and collective excitation [91]; and threshold energy
derived from simulation of specic experiments for induction of single strand breaks with a
single base pair resolution information [92,93]. Although all three categories listed above
suggest a range of values for induction of SSBand/or DSB, intrinsically, they do not provide
elucidation of the biochemical mechanism leading to DNA damage/strand breaks. Of the
three categories, the rst one is primarily based on microdosimetry and track structure cal-
culations of energy depositions in target volumes pertaining to DNA or higher-order struc-
tures. In such calculations, one usually seeks quantities of energy depositions and spatial
dimensions per unit dose of ionizing radiation as a function of energy deposited in the vol-
ume under consideration by a single particle track that do, or do not, correlate with the
observed biological eectiveness. Correlation of local energy depositions, in terms of their
clustering properties, have revealed that typical energy depositions of the order of tens of
electron volts, in DNA-size targets, predominantly lead to single strand type breaks, and
damage from energy depositions of the order of 100 eV is predominantly of double strand
break type [68].
An alternative way of using jump-the-detail provided by the Monte Carlo track
structure approach is to examine the way in which energy is deposited in the volume of
reaction of sugarphosphate, purine, and pyrimidine bases [97]. To convert these energy
depositions into damage requires an understanding of the relationship between track events
(ionizations, excitations, and radical products) and their actions on DNA. To establish
such a coupling, modeling of an experiment in which single strand breaks induced by the
decay of
125
I incorporated into the plasmid DNA was originally carried out by Charlton
and Humm [92]. It was found, assuming an energy deposition greater than 17.5 eV in the
sugarphosphate moiety induced a single strand break (SSB), that the experimental dis-
tribution of SSB could be reproduced [89,92,93]. The distribution of energy depositions
along the DNA could now be converted into distributions of SSBs and DSBs. Use of such a
technique has provided reasonable agreement with experimental data. Similar jump-the-
detail modeling has also been carried out by other workers using dierent values for the
threshold energy needed for induction of a SSB. These include a single ionization [94],
energy deposition greater than ionization threshold 10.5 eV [39], 1013 eV energy de-
position [77], collective excitation energy 21.6 eV [95], and DNA dipole oscillator strength
30 eV [91]. It should not be surprising that all the values listed above, used in the respective
modeling work, produce agreement with the experimental values of total yield of strand
breaks. However, such overall agreements may not necessarily provide a unique description
of the spectrum and complexity of DNA damage produced in the hit region of the genome.
The spectrum of DNA damage produced by radiation track becomes crucially important
when one is interested in kinetic modeling of DNA damage and repair and relating results
of track structure calculations for dierent radiations and doses to corresponding observed
biological eects.
The second parameter in jump-the-detail method is the eciency of the reaction of
hydroxyl radical with DNA leading to strand breakage. Hydroxyl radicals are important
oxygen species, which upon reaction with DNAproduce strand break and base damage, and
their contribution to the total yield of damage is a function of the hydration level sur-
rounding the DNA. The more dilute the solution, the longer the lifetime of the radicals. The
environment of the cell contains high levels of scavengers that reduce the number of radicals
available for reaction with DNA. In a cell mimetic condition, a diusion distance of 46 nm
has been used [79]. Only a few quantitative experimental reports are available that provide
values for the probability of induction of DNA strand breaks by OH radicals, as not all
radicals lead to strand breaks [96,98]. Based on the ndings of experimental work the prob-
ability of SSBformation per OHradical has been considered to be 0.12 F0.01 upon reaction
with DNA [79,99]. It is usually considered that the eciencies of other radical species to
produce a strand break are negligible. In a number of studies, probability of OH radical for
induction of SSB has been assumed as unity [39,100,101].
An alternative method to investigate DNA strand breakage by OH radicals considers
the surface accessibility of hydrogen atoms of the DNA backbone [102]. The solvent acces-
sibility is
f
80% for the sugarphosphates and
f
20% for the bases. This method allows a
more direct determination of reaction of OH radicals with the individual deoxyribose hy-
drogens [103,104]. Recent studies show trends in reactivity of OH radicals closely follow the
accessibility of the solvent to various deoxyribose hydrogens [105,106].
Production of strand breaks by very low energy electrons (525 eV) in thin solid DNA
lms using ultrahigh vacuum systems have been reported in a number of studies [107109].
Such studies have demonstrated the eciencies of low energy electrons and photons to
induce DNA damage. In the vacuum ultraviolet (UV) region, examination of experimental
data [86,110,111] shows that the induction of strand breaks depends on the absorption
spectrum of the components in the medium and the sensitivity spectrum of DNA [112].
Introduction of a variable with the wavelength for the induction of SSB by OH radicals, in
conjunction with a xed value for the quantum eciency for the production of OH radical
(u
OH
=0.04), allows an interpretation of the vacuum UV sensitivity spectrum for induction
of SSB in aqueous system [112].
5.3. Base Damage
The measurement and quantication of base damage depends on environmental conditions,
cell type, and the technique used. For the purpose of modeling, an experimentally related
quantity is the ratio of the yield of base radicals to sugarphosphate damage. A preliminary
estimate of the ratio of base to sugarphosphate damage can be calculated either by inde-
pendently counting all hits that lead to damage in bases or sugarphosphates, or by counting
those segments of DNAthat contain at least one base damage and two strand breaks, one on
each strand within V10 bp (Fig. 3C). The latter ratio should be comparable with the experi-
mentally measurable quantity. In the absence of rigorous experimental data on energetic
of base damage, the preliminary calculations of the yield of base damage have been obtained
by considering a similar kinetic as those used for the production of single strand breaks. A
probability of 0.8 was assumed for induction of base damage from the reaction of OH rad-
icals with the nucleobases. For direct damage, recent experimental data by Abdoul Carime
et al. [113] and modeling by Watanabe and Nikjoo [76] show a threshold energy of
f
10 eV
for the activation of a base moiety for direct energy deposition to produce an electron adduct
or the protonated form of the base.
5.4. Summary
Current jump-the-detail technique of modeling DNA damage requires at least two essential
parameters: (1) energy for direct induction of SSB, which has been determined from mod-
eling a well-controlled experiment with internal Auger emitters, and (2) probability for
induction of a SSB by reaction of an OH radical with DNAa value of 0.12F0.01 was
adopted, based on experimental ndings in a cell mimetic condition. Our data suggests a
threshold value of 17.5 F 2 eV as the most probable value for the energy deposited in the
volume of a sugarphosphate by a single track for the induction of SSB by direct mecha-
nism. Based on these assumptions, Fig. 4 shows the yields of SSB and DSB as the function
of LET and in comparison with experimental observations. A wide range of energies, from
10 to 30 eV, have been used in various modeling works. Such a broad range on the choice of
the threshold energy for induction of a SSB emanates from the type of experimental data
used for normalization of calculated data and dierences in track structure codes. For
estimation of base damage, similar kinetics as those for induction of SSBhave been used, viz,
17.5 eV for induction of base damage by direct energy deposition and a probability of 0.8
from reaction of OH radicals, but in the light of more recent reports [76,113], these values
may have to be revised.
6. SPECTRUM OF DNA DAMAGE
Earlier in this chapter, a number of questions were considered on correlation between bio-
logical eectiveness of ionizing radiation and severity or the quality of damage. In this
respect, the hypothesis put forward in the 1980s by two of its protagonists [15,16] articulated
that the quality of damage by ionizing radiation is a major factor in determining the survival
and mutagenecity of the cell. Evidence in support of the hypothesis has come mainly from
modeling and calculations [32,68,114,115].
Figure 4 Yield of single and double strand breaks as a function of LET for ions.
In essence, the hypotheses Clustered Damage and the Locally Multiply Damaged
Sites attempt to correlate the frequencies of various types of DNA damage with the
observed biological lesions. The approaches were originally based on the classication of
damage either by energy deposition or by number of ionizations and reactions of hydroxyl
radicals in DNA. Brenner and Ward [116], using a track structure approach, concluded that
yields of clusters of multiple ionizations within 23 nm sites correlate well with observed
yields of double strand breaks. Goodhead [28,114], using the database of frequencies of en-
ergy depositions in small volumes of dimensions similar to important biological structures
for a range of radiations, deduced a classication based on the size of energy deposition
in the target, which could correlate with particular biological eects. The classication
includes four classes of initial physical damage in terms of sparse energy depositions of
a few tens of electron volts in DNA producing simple damage predominantly of single
strand type, moderate energy depositions of nearly 100 eV in DNA producing damage
predominantly of double strand break type, large energy depositions of the order of 400 eV
in nucleosome DNA producing multiple DSB and protein cross-link, and very large clus-
ters of
f
800 eV pertaining to chromatin size targets producing large deletion and gross
damage. With the emergence of more sophisticated techniques in modeling and quanti-
cation of damage in DNA, it is now possible to estimate the spectrum of DNA damage in
terms of complexity of damage for low and high-LET radiations [32,75,79,81,87,91,117
122].
Simple experimental approaches to this problem recently started postulate that the
repair of clustered DNA damage leads to conversion of nonlethal lesions, e.g., dihydrothy-
mine, or mutagenic lesions, such as 8-OxoGuanine, into lethal double strand breaks. These
early experiments have studied kinetics and inuence of excision of base lesion within clus-
tered DNA damage by E. coli and nuclear extracts [27,123129].
For a graphical and quantitative demonstration of some of the ideas expressed above,
data are presented for DNA damage induced by 3.2 MeV alpha particles. Patterns of energy
depositions in individual DNA segments were analyzed for induction of strand breaks and
base damage using an atomistic model of B-DNA. Fig. 5 shows a few examples of the hit
region of DNA by tracks of 3.2 MeV alpha particles. The indicates strand-break
induction by direct energy deposition. The numerals/symbols indicate the damage by direct
energy depositions that did not lead to strand break. Hs are the sites of reaction of OH
radical with the DNA leading to strand break. Track structure calculations have shown that
a substantial proportion of the dose,
f
30% from low-LET irradiation, is deposited by low-
energy secondary electrons [115] that are ecient in producing clustered damage at nano-
meter scale [68,115]. Fig. 6 shows the frequency of complex double strand breaks. The data
shows with increasing LET the proportion of complex double strand breaks increases
reaching to more than 70%. The data presented in Fig. 6 do not include the contribution
of base damage. On the assumption that base damage more frequently occurs than strand
breaks (Table 1), it is likely that a high proportion of double strand breaks contain addi-
tional base damage.
Table 5 provides calculation of strand breakage with the additional information on
the number of base damages for 3.2 MeV alpha particles. The left-hand side of Table 5
presents frequencies of strand breaks containing none or at least one or more base damage
on purine or pyrimidine bases. The right-hand side of the table shows a more detailed
analysis of the frequencies of breaks in italic-bold. For example, 12.5% of 58% DNA seg-
ments with no strand breaks contains two base damages. Of these, 3.6% (1.7+1.9) are
located within 3 bp of each other, while 8.9% (4.3+4.3) are located at distances >3 bp from
each other.
Figure 5 Individual examples of simulated sites of damage induced by 3.2 MeV alpha particles in
DNA. In each example, the outer and inner rows represent the sugarphosphate moieties and the
pairs of bases, respectively, with single base pair resolution (dots). An or H represent energy
deposition or reaction of hydroxyl radical leading to induction of a single strand break or base
damage. A indicates hit sites that did not lead to strand breaks (SB) or base damage (BD).
Nomenclature: no strand break (No SB); single strand break (SSB), (SSB
+
), (2SSB); double strand
break (DSB), (DSB
+
), (DSB
+
).
6.1. Summary
Complex damage presents an increased challenge to the repair processes operating in the
cell and is postulated to be largely responsible for the greater biological eectiveness of
high-LET radiations.
Experiments have shown slower repair of double strand breaks by high-LET

radiations [66,152,226].
Modeling and calculations show that with increasing LET, there is a shift toward
a greater complexity of clustered damage in DNA [30,81,87,119].
Figure 6 Fraction of complex double strand breaks for protons (open squares), alpha particles
(solid squares) as a function of LET, and electrons (triangle). The contribution of base damage is not
included in these calculations.
Table 5 Frequency Distribution of a Number of Base Damage
3.2 MeV alpha particles
No. of Base BDV3 bp BD>3 bp
Damage 0 1 2 3 4 z5 adj opp adj opp Total Hits
Model 1 No break 31.4 12.5 6.9 3.7 3.5 1.7 1.9 4.3 4.6 58.0
Model 2 SSB 5.1 4.8 4.0 4.8 2.6 2.6 1.1 0.9 1.3 1.6 23.9
Model 3 SSB+ 0.1 0.5 1.3 1.0 1.0 2.4 0.1 0.1 0.0 0.3 6.3
Model 4 2SSB 0.2 0.1 0.1 0.2 0.3 0.8 0.0 0.1 0.0 0.0 1.7
Model 5 DSB 0.2 0.6 0.7 1.1 1.0 1.7 5.3
Model 6 DSB+ 0.1 0.1 0.2 0.6 1.0 1.7 3.6
Model 7 DSB++ 0.0 0.1 0.1 0.0 0.2 0.8 1.2
Ratio of base to sugar/phosphate damage = 3.4.
Inclusion of base damage substantially increase the proportion complex damages

(both SSB and DSB) [80,81,87].
Experiments as well as calculations show the yield of strand breaks per unit dose
is nearly constant over a wide range of LETs [75,80,81].
The majority of strand breaks is of simple type containing a single strand break;
however, if base damage is taken into account, the majority of single strand breaks
appears to be complex [81].
For low-LET radiations, nearly 30% of dose is deposited by low-energy secondary

electrons [115].
Low-energy electrons are ecient in producing clustered damage at DNA level

[115].
These clusters occur with high frequencies per unit dose [68].
A high proportion of double strand breaks (

f
20%) produced by low-LET rad-
iation are of complex origin [7981].
A signicant proportion of non-double strand breaks are of complex type (Table

5).
Including the base damage,

f
50% of all double strand breaks contain additional
breaks [7981].
For high-LET radiations, per unit dose fewer regions of genomes are hit, i.e.,
smaller number of tracks per unit dose (Table 1).
For high-LET radiations, reaching

f
70% of all double strand breaks contain
additional strand breaks, if base damage is included, this proportion increases to
f
90% [79,81].
7. RADIOPROBING OF NOVEL DNA STRUCTURES
Since the determination of the double-helical structure based on x-ray ber data and chemi-
cal modeling [130,131], considerable eort has been made to obtain an ever more detailed
picture of the conformation(s) of DNA alone and in complexes with drugs or protein. The
x-ray crystallographic analysis of mono- and dinucleotides leads to the atomistic deter-
mination of the structure of the bases, sugar, and base pairs, while x-ray ber diraction
data have been used to determine the overall shape of the various helical families [132,133].
Other techniques for probing DNA structures include enzymes and chemicals [134]. Crys-
tallographic studies need production of large and well-dened crystals that are not always
possible. Enzymes and chemical methods have been used to study the local structural per-
turbation in DNA from local reactivity to enzyme cleavage and chemical modication.
Enzymatic probes are mostly nucleases that probe accessibility of the enzyme at each
phosphodiester bond. There is a wide range of chemical probes available for the study
of DNA structures in the neighborhood of the bound drug molecule, proteins, and base
mismatches. Rydberg et al. [40] reported a new method for probing the conformation
of chromatin in living cells. They used x-ray and accelerated heavy ions, and from the char-
acteristics of patterns of radiation-induced strand breaks the authors proposed a zigzag
model of chromatin structure in eukaryotic cells. In addition to stable structures of DNA,
there is an important class of DNAs that cannot easily be obtained in a single crystal such
as three- and four-stranded structures. This section provides a short description of a new
method for the study of DNA structures such as triplex and quadruplex DNAs using Auger
electrons as a probing tool [41].
Auger electrons have extensively been used as a tool in molecular and biophysical
aspects of radiation action at DNA and cell level. Historically, in fact, although Auger
electrons was discovered in 1925 by Pierre Auger, it was not long after that two French
biologists [135] suggested its use as a magic bullet in radiation therapy.
The ability of nucleic acids to form triple helical structures may play an important role
in mechanisms of DNA recombination and gene transcription, and also represents an
important new approach to sequence-specic drug targeting [136,137]. Although triple
helices have been known for over 40 years [138], details of their molecular structure still
remain elusive. Early models of triple helices, based on ber diraction data, suggested an A-
form conformation [139], while more recent nuclear magnetic resonance (NMR) and
modeling studies support the view that these structures have more in common with the B-
form of duplex DNA [136,140]. In this study, we used a computational method to simulate
the damage to a triplex DNAresulting fromAuger electrons emitted through the decay of an
incorporated
125
I. In comparing theoretical frequency distributions of single strand breaks
with the experimental data [141], the results are very sensitive to the conformation of the
triplex model used. We nd that the best t to the experimental data results from using a
hybrid triplex model, in which the base-step geometry is A-like, while the sugar puckers
adopt the B-like C
2
V -endo conformation.
Radionuclide such as
125
I decay by emitting a dense cascade of electrons (Auger elec-
trons), most of which are short range with energies less than 1 keV[142]. The release of these
electrons results in a highly charged residual atom and the deposition of a large amount
of energy near the site of decay. In recent years, it has become possible to position Auger
emitting radionuclide at specic locations along a dened DNA target molecule [143146].
This has been carried out either by direct incorporation of, e.g., iodine-labeled deoxynu-
cleotide, or by binding of a
125
I-labeled sequence-selective DNA ligand. After allowing
the accumulation of decay in the target, resulting in DNA strand breaks and base damage,
DNA sequencing techniques have been used to locate the positions of strand breaks relative
to the site of decay with a precision of a single nucleotide base. Previously, we and others
have developed Monte Carlo track structure methods to simulate the process of DNA
damage [92,93,100,147] and obtained frequency distributions of strand breaks induced in
plasmid DNA labeled with an Auger emitting radionuclide that is in good agreement with
experimental data. These calculations have shown that most damage occurs directly because
of the emitted electrons within about 10 base pairs either side of the decay site, while the
damage caused by hydroxyl radicals generated in the water surrounding the DNA is mainly
long range, only making a minor contribution to DNA damage near the site of decay [93,
148]. These results prompted us to consider the approach as a method for structure deter-
mination, or at least evaluation, in the neighborhood of the site of decay. Panyutin et al.
[141,149151] have published the results of experiments measuring the prole of DNA
damage induced in the polypurinepolypyrimidine region of the nef gene of the human
immunodeciency virus through interaction with a triplex forming oligonucleotide labeled
with
125
I. The experiment [141] was the rst attempt to use the antigene approach to deliver
radio nucleotides to a target DNA and so produce sequence-specic DNA breaks. Nikjoo
et al. [41] have reported on the modeling of this experiment and the sensitivity of the results
to structural parameters. As a result of comparing calculated frequency distributions of
fragment lengths with those obtained from the experiment, it was concluded that currently
accepted models for triplex structure are not optimal, and propose a modied structure
that better ts the radioprobing results, while maintaining agreement with the ber dif-
fraction and NMR data.
8. RADIATION BYSTANDER EFFECT
Radiation-induced genomic instability and bystander eects are now well-established con-
sequences of exposure of living cells to ionizing radiation. Cells not directly traversed by
radiation may still exhibit radiation eects. This phenomenon, known as bystander eect,
has become a major activity in radiation biology and in some cases has challenged the
conventional wisdom. An example is the currently accepted models used for low-dose
extrapolation of radiation risks. The currently used models assume that cells in an irradiated
population respond individually rather than collectively. If bystander eects have implica-
tions for health risks estimates from exposure to ionizing radiation, then the question of
whether this is a general phenomenon or solely a characteristic of a particular type of cell and
the radiation under test becomes an important issue.
Doseresponse curve for all solid cancers based on atomic bomb survivors data indi-
cate a linear form down to doses as low as 50 mSv. However, risk estimates for radiation-
induced oncogenesis at very low doses (<50 mSv), at a region where direct experimental
observations are not available, are usually extrapolated from high doses of ionizing radi-
ation using a linear nonthreshold model [14,153]. The validity of this approach is still a
subject of investigation and discussion. There are a number of factors aecting the shape of
doseresponse curve at low doses of irradiation including low-dose hyper-radiosensitivity
[154], adaptive dose response [155], genomic instability [156,157], and more recently by-
stander eect [9]. The latter is considered as one phenomenon that may be of signicant
importance in inuencing the shape of doseresponse curves.
The bystander eect has been observed for a variety of biological end points such as
cell survival [158 159], mutation [160162], sister chromatid exchanges [163], cell transfor-
mation [164,165], micronucleated and apoptosis [166], gene expression [167], and radiation
genomic instability [168170].
Theoretical and modeling works have also been recently published [171173]. The
model of Brenner et al. [171] is based on a binary phenomenon in a small sensitive sub-
population of cells. Their model suggested that the bystander eect is important only at
small doses. The papers published by Nikjoo and Khvostunov [172,173] investigated
whether the bystander eect depends on the mode of irradiation (broad beamor microbeam
systems), hypothesizing a particular mechanism of cell-to-cell communication assuming the
signal has a protein-like nature, and is communicated by diusion in the medium. The
authors investigated the bystander phenomenon for the broad beam and microbeam
irradiation systems for cell inactivation and oncogenic cell transformation in C3H10T1/2
cells. The general conditions for the bystander eect to dominate were formulated based on
the fraction of hit and nonhit cells. The model shows the bystander phenomenon is the
dominant factor at low doses in the case of the broad beam irradiation, while for the
microbeam irradiation both at low and high dose.
9. TRACK STRUCTURE SIMULATION
This section provides a brief description of theoretical bases of the Monte Carlo track
simulation codes we have developed for electrons and ions. Our database of Monte Carlo
track simulation codes include: electrons (code kurbuc 10 eV to 10 MeV) [174], protons
(lephist 1 keV to 1 MeV) [175], alpha particles (leahist 1 keV to 8 MeV) [176], all ions
(pits 0.3 MeV/u to GeV) [74] and the code chemkurbuc for description of prechemical and
chemical stages of electron track in liquid water (unpublished).
A complete model of track structure consists of descriptions for inelastic and elastic
interactions. As charged particles pass through matter, they lose energy primarily through
collisions with bound electrons. Ionization cross sections for all projectile and secondary
electron energies are needed to follow the history of an incident particle and its products,
covering all range of energies transferred in individual collisions. Elastic interactions take
place when the incoming particle interacts with the atomic eld and is deviated from its
path by a small angle without the loss of energy.
Not all cross sections are available for materials of interest in radiation biology. Cross-
section data for liquid water are scarce, as measurements are either impractical or very dif-
cult. For practical reasons, we use water vapor cross sections for total and partial ion-
ization and excitation cross sections. In general, a Monte Carlo track structure code requires
at least eight sets of cross sections: (1) total ionization, (2) total excitation, (3) total elastic
scattering, (4) partial ionization cross sections for ve electron orbitals of water molecule,
(5) partial excitation cross sections for various excited states, (6) secondary electron energy
spectrum, (7) angular distribution of elastic scattering, and (8) angular distribution of sec-
ondary electrons.
9.1. Electrons
Ionization Cross Sections
Inelastic cross sections for ionizations and excitations were compiled for low- and high-
energy electrons. The experimental ionization cross sections for water vapor in the energy
range of 10 eV to 10 keV [177181] were least-squares tted as shown by a solid line in
Fig. 7 using a model function:
r
exp
c at
r
e
b
1
tb
2
t
2
1
t ln
T
15
in which the unit of r is 10
16
cm
2
and that of T, the particle kinetic energy, is eV. The
tting parameters are given by
a 2:07201 b
1
0:271302 b
2
0:119638 r 1:46521 c 0:074
At energies higher than 10 keV, ionization cross sections were calculated using Selt-
zers formula [183]. Seltzers formula gives the partial ionization cross sections for ve
molecular orbitals of water. The total ionization cross sections in the energy range of 10 keV
to 10 MeV were obtained by summing up all the partial cross sections (Fig. 8).
Excitation Cross Sections
There are various modes of excitation for T > 7.4 eV. As reported experimental excitation
cross sections are fragmentary, we used the compiled data of Paretzke [184] that includes
all the major excitation modes. Paretzke tted the experimental cross sections for the 10
major individual states using a model function:
r
exc
U
3
T
4pa
2
0
R
T
M
2
a
ln
4c
s
T
R
2
in which U
3
(T) is an empirical correction factor of the form
U
3
T 1 e
0:25T=E
a
1
3
where a
0
is the Bohr radius = 0.529310
8
cm, and R is the Rydberg constant = 13.6 eV.
Parameters M
a
2
, E
a
, and c
s
for each level are given by Paretzke. An additional three levels
were tted by the analytical model given by Gren and Stolarski [185]. Table 6 lists eight
major excitations and excitation energies considered in this work. The total excitation
cross section in the energy range of 10 eV to 10 keV was obtained by summing up all the
individual cross sections. The total excitation cross section for the high-energy region up
to 10 MeV is given by an empirical formula derived from the Fano plot, with tting pa-
rameters determined by Berger and Wang [186]:
r
exc
4p
a
0
137b
_ _
2
12:30 1:26 ln
b
2
1 b
2
b
2
_ _ _ _
4
in which b is the ratio of electron velocity to the velocity of light. Total excitation cross
section in the energy range of 10 eV to 10 MeV is shown in Fig. 8.
Figure 7 Experimental total ionization cross section as a function of electron energy. The solid line
is the least-squares t to all data [177181]. The calculated data of Dingfelder et al. [182] for liquid
water is plotted for comparison.
Elastic Scattering Cross Sections
Elastic scattering cross sections were calculated using the Rutherford formula, taking into
account the screening parameter given by Moliere [187]. The dierential cross section (dr/
dX)
el
and total cross sections r
el
for each molecule are represented by
dr
dX
_ _
el
ZZ 1r
2
e
1 b
2
b
4
1
1 cosh 2g
2
5
r
el
pZZ 1r
2
e
1 b
2
b
4
1
gg 1
6
Figure 8 Total cross sections for ionization, excitation, and elastic scattering of electrons in water
vapor in the energy range of 10 eV to 10 MeV.
Table 6 Excitations and Transition
Energy Considered in the Kurbuc Code
Excitation state Energy (eV)
A
1
B
1
7.4
B
1
A
1
9.7
Diuse band 13.3
Rydberg (A+B) 10.0
Rydberg (C+D) 11.0
H* Lyman a 21.0
H* Balmer a 21.0
OH* 9.0
The screening parameter g is given by
g g
c
1:7 10
5
Z
2=3
1
ss 2
7
where the eective atomic number of the water molecule, Z, was assumed to be 7.42, r
e
is the classical electron radius, s = T/m
0
c
2
is the kinetic energy in units of the electron
rest mass.
g
c

1:198 T < 50keV 8a
1:13 3:76
Z
137b
_ _
2
Tz50keV 8b
_
_
The parameter g
c
was determined by the least-square tting to the experimental data
[188191]. Total elastic scattering cross section in the energy range of 10 eV to 10 MeV is
shown in Fig. 8. Angular distributions for elastic scattering below 1 keV were obtained by
direct sampling of various experimental data [189,190,192].
Secondary Electrons
The calculation of the secondary electron spectrum was carried out using the method of
Seltzer [183]. For the jth orbital of a molecule, the cross-section dierential in kinetic
energy w of the ejected electron is written as the sum of close and distant collisions.
dr
j
dw

dr
j
c
dw

dr
j
d
dw
9
The rst term describes collision between two electrons.
dr
j
c
dw

2pr
2
e
m
0
c
2
n
j
b
2
T
T B
j
U
j
1
E
2

1
T w
2

1
T
2
s
s 1
_ _
2
1
ET w
2s 1
s 1
2
G
j
_ _
10
G
j

8U
j
3p
1
E
3

1
T w
3
_ _
tan
1

y
p

y
p
y 1
y 1
2
_ _
11
in which n
j
is the number of electrons in the orbital, B
j
is the orbital binding energy, U
j
is the
mean kinetic energy of the target electron in the orbital, E is the energy transfer (=w+B
j
)
and y =w/U
j
. Table 7 shows electron number, binding energy [193], and kinetic energy [194]
Table 7 Electron Number n
j
, Binding Energy B
j
, and Kinetic
Energy U
j
for the jth Orbital of a Water Molecule
j Orbital n
j
B
j
(eV) U
j
(eV)
1 1b
1
2 12.62 61.91
2 3a
1
2 14.75 59.52
3 1b
2
2 18.51 48.36
4 2a
1
2 32.4 70.71
5 1a
1
2 539.7 1589.5
for the jth orbital of a water molecule. The second term is described in terms of the
interaction of the equivalent radiation eld with the orbital electrons.
dr
j
d
dw
n
j
IEr
j
PE
E 12
where r
PE
( j)
is the photoelectric cross section for the jth orbital (per orbital electron), for an
incident photon of energy E, I(E) is the virtual-photon spectrum. Fig. 9 shows the dis-
tribution of secondary electrons for 1 and 10 keV primary electrons calculated by Eqs.
(10)(12) in comparison with the calculated data of Paretzke [184] and the experimental data
of Vroom and Palmer [195] and Bolorizadeh and Rudd [180].
Angular distribution of secondary electrons for the ejected energy w z 200 eV was
calculated using the kinematical relationships
cos h
wT 2m
0
c
2
Tw 2m
0
c
2
13
For w<200 eV, regardless of the primary electron energy, angular distributions were ran-
domly sampled using the experimental data of Opal et al. [196].
Monte Carlo Electron Code
The Monte Carlo track structure code kurbuc simulates electron tracks in water vapor for
initial electron energies 10 eV10 MeV [174]. The code kurbuc provides all coordinates of
Figure 9 Energy spectra of secondary electrons for 1 and 10 keV electrons produced by the Seltzers
theory in comparison with the calculations by Paretzke [184] and the experimental data [180,195].
molecular interaction in water vapor, amount of energy deposited at each event, and the type
of interaction at each event. Using tracks generated by kurbuc, various physical parameters
such as penetration distances, W values, radial distributions of interactions, point kernel,
and frequencies of energy deposition in small cylindrical targets can be obtained. As an
example of track structure analysis, Fig. 10 shows results of W values of low-energy elec-
trons in water vapor. Wvalues are derived from scoring the number of electronH
2
O
+
pairs
because of ionization process. Calculated W value at the high-energy limit agrees with the
experimentally determined asymptotic limit of 30.4 eV.
9.2. Ions
Ionization Cross Sections
Here we use the termions limiting to protons H
+
and alpha particles He
2+
. For fast ions,
the majority of energy is transferred in ionizing collisions, resulting in energetic free
electrons and the potential energy of residual ions. Ionizing collisions involving bare ion
projectiles, unless they are very slow, can be treated by using a classical description for the
trajectory of the projectile with a quantal description of the target. When fast ions slowdown
around the Bragg peak (0.3 MeV/u), interactions involving electron capture and loss by the
moving ions become an increasingly important component of the energy loss process.
Detailed descriptions for charge transfer processes will be given in Sec. 9.3.
Total ionization cross sections for bare ions (H
+
and He
2+
) were obtained by tting
polynomial functions to the experimental data given by Rudd et al. [198] for protons, and
Figure 10 Calculated W values for electrons in water vapor as a function of the initial energy of
electrons in comparison with the data of Combecher [197].
Rudd et al. [199] and Toburen et al. [200] for alpha particles.
r
ion

j
c
j
log
10
T
jl
14
in which T is in keV/u. Where data were lacking, extrapolation was made by taking into
account the reproducibility of stopping powers. Fig. 11 shows total ionization cross sections
of water vapor by H
+
(left) and He
2+
(right).
Excitation Cross Sections
There are no experimental data of excitation cross sections for proton and alpha particle
impact for water. The proton cross sections were obtained by scaling of the electron exci-
tation cross sections for high-energy protons >500 keV [201]. For the lower-energy regions,
the semiempirical model developed by Miller and Green [202] was adopted, which is based
on the electron impact excitation. They assumed an analytical function for each excited level
of the form
r
e

r
0
Za
X
T W
v
J
Xv
T
Xv
15
where r
0
=10
16
cm
2
, Z=10, and the parameters W, a, J, X, and v for 28 excitation states are
given in Table 3 of Ref. 202. We assumed cross sections for protons can be applied to the
impact excitation cross sections for alpha particles as shown in Fig. 11.
Figure 11 Total cross sections due to proton (left) and alpha particle (right) impact on water vapor.
Total ionization cross sections were obtained by tting polynomial functions to the experimental data
[198200]. The curve for excitation was assumed to be the same between protons and alpha particles.
Elastic scattering was evaluated by the classical mechanics trajectory calculations [Eqs. (16) and (17)].
Elastic Scattering Cross Sections
High-energy ions proceed along a straight-line trajectory. However, the eects of elastic
nuclear collisions will become more prominent in the low-energy region. Elastic collisions
transfer little or no energy but can have a signicant eect on the spatial character of the
track structure at very low energies. Also, the nuclear energy loss cannot be neglected <10
keV/u. Nuclear elastic scattering was evaluated using the classical mechanics trajectory
calculations taking into account the screening by atomic electrons [203]. For a particle
scattered in a central potential V(r), the deection angle h is obtained as a function of the
impact parameter p [204] such that
h p 2
_
l
r
min
p
r
2
1 Vr=T
cm
p
2
=r
2
_ dr 16
where r
min
is the distance of closest approach, T
cm
is the particle energy in the center-of-mass
system. Equation (16) was numerically solved using procedures given by Everhart et al.
[205]. The dierential elastic scattering cross section can be obtained by the classical rela-
tionship [206],
dr
el
dX

p
sin h
dp
dh
17
To reduce the divergence of the total cross section, which is obtained by integral of Eq. (17),
the cuto angle was set so as to limit the increase in the scattering probability at low scat-
tering angle. Fig. 11 shows calculated total cross section for H
+
(left) and He
2+
(right).
Secondary Electrons Distribution
Energy spectra of secondary electrons ejected by ion impact were calculated using the
empirical model given by Rudd [207]
dr
j
e
de

S
B
F
1
F
2
w
1 w
3
f1 expaw w
c
=vg
18
where w=e/B, v =(T/kB)
1/2
, w
c
=4v
2
2vR/4B, S =4pa
2
0
Nz
2
(R/B)
2
, e =electron energy,
B = binding energy for each orbital, a
0
= 0.52910
8
cm, N = electron number in orbital,
z = charge of the projectile nucleus, and R = 13.6 eV,
F
1
v
L
1
H
1
L
1
C
1
v
D
1
=1 E
1
v
D
1
4
H
1
A
1
ln1 v
2
=v
2
B
1
=v
2
_
19
F
2
v
L
2
H
2
=L
2
H
2
L
2
C
2
v
D
2
H
2
A
2
=v
2
B
2
=v
4
_
_
The tting parameters for water vapor are given by Rudd et al. [208]
A
1
= 0.97 B
1
= 82 C
1
= 0.40 D
1
= 0.30 E
1
= 0.38
A
2
= 1.04 B
2
= 17.3 C
2
= 0.76 D
2
= 0.04 a = 0.64
This model gives the single dierential cross sections (SDCS) for secondary electron
production by ion impact, and also the partial ionization cross sections for each orbital. The
boundary energy for energetic secondary electrons generated by ionization was determined
as 1 eV. Fig. 12 shows the randomly sampled energy spectra of ejected electrons for various
energies of H
+
(left) and He
2+
(right) in comparison with experimental data [200,209].
Experimental angular distributions of electrons ejected from water by H
+
impact are
given by Bolorizadeh and Rudd [209], and by Toburen and Wilson [210] in the energy range
between 15 keV and 1 MeV. Available experimental angular distributions for He
2+
are lim-
ited. To cover the broad ion energy range, available H
+
data were used assuming that dif-
ferences of angular distributions between dierent ions are not very large. Interpolation was
made for the intermediate energies of electrons and ions.
9.3. Low-Energy Ions
Charge Transfer Cross Sections
Charge transfer can produce residual ions without the release of free electrons, and free
electrons can be ejected fromthe moving ion (or neutral) with no residual ions being formed.
Charge transfer cross sections are generally designated as r
if
where i is the initial and f
is the nal charge state of the moving particle. Table 8 lists the interactions for low-energy
proton (H
+
) and neutral hydrogen (H
0
) with water. Table 9 lists the interactions for low-
energy He
2+
, He
+
, and He
0
. To develop track structure models, cross sections are needed
for both electron capture and electron loss. For incident ions with speeds comparable to or
Figure 12 Randomly sampled energy spectra for secondary electrons ejected by proton (left) and
alpha particle (right) impact in comparison with experimental data [200,217]. The lines are the results
obtained from sampling 5 10
5
times using calculated data from the Rudd model [Eqs. (18) and
(19)].
lower than the orbital speeds of bound electrons in the target, the capture of electrons from
the target is a signicant mechanism for the ionization of the target without production of
secondary electrons. If the projectile is a dressed ion (i.e., an ion bearing one or more
electrons), a collision can eject electrons from either the projectile or the target. For a fast
projectile, one can consider the projectile as a simple collection of a nucleus and electrons
traveling together at the same speed. After the charge transfer, the dressed ion or the neutral
atom becomes either stripped or ionizes a water molecule. In the former case, stripped ion,
an electron is ejected in a forward direction with nearly the same velocity as the projectile. In
the latter case, ionization of water molecule without changing the ionic charge state, an
electron is ejected with a dierent distribution of electron energy and with a similar ejection
angle as that of the bare ions.
Fig. 13 shows charge exchange cross sections based on available experimental data
for H
+
and H
0
(upper left) [211,212], He
2+
(lower left) [199], He
+
(lower right) [213,214],
and He
0
(upper right) [214,215]. There is a probability of two-electron transfer for helium
atom, such as r
20
and r
02
. Total cross sections for electron capture r
10
for H
+
and
electron loss r
01
for H
0
were evaluated using the analytical functions developed by Miller
and Green [202]. Cross sections for He ions were least-square tted by a simple polynomial
function similar to Eq. (14). Smooth extrapolation was carried out where the experimental
Table 8 Interactions for Low-Energy H
+
and H
0
with Water
Interactions H
+
+ H
2
O! H
0
+ H
2
O!
(i) Elastic scattering H
+
+ H
2
O H
0
+ H
2
O
(ii) Target ionization H
+
+ H
2
O
+
+e H
0
+ H
2
O
+
+ e
Target excitation H
+
+ H
2
O
*
H
0
+ H
2
O
*
(iii) Electron capture H
0
+ H
2
O
+
(r
10
)
Electron loss H
+
+ e + H
2
O (r
01
)
(iv) Electron capture and
target ionization
H
0
+ H
2
O
2+
+e
Electron loss and
target ionization
H
+
+ e + H
2
O
+
+ e
Table 9 Interactions of Low-Energy He
2+
, He
+
, and He
0
with Water
Interactions He
2+
+ H
2
O! He
+
+ H
2
O! He
0
+H
2
O!
(i) Elastic scattering He
2+
+H
2
O He
+
+H
2
O He
0
+H
2
O
(ii) Target ionization He
2+
+H
2
O
+
+e He
+
+H
2
O
+
+e He
0
+H
2
O
+
+e
Target excitation He
2+
+H
2
O* He
+
+H
2
O* He
0
+H
2
O*
(iii) Two-electron capture He
0
+H
2
O
2+
(r
20
)
One-electron capture He
+
+H
2
O
+
(r
21
) He
0
+H
2
O
+
(r
10
)
One-electron loss He
2+
+e +H
2
O (r
12
) He
+
+e +H
2
O (r
01
)
Two-electron loss He
2+
+e +e +H
2
O (r
02
)
(iv) One-electron capture
and target ionization
He
+
+H
2
O
2+
+e He
0
+H
2
O
2+
+e
One-electron loss and
target ionization
He
2+
+e +H
2
O
+
+e He
+
+e +H
2
O
+
+e
data were lacking. Fig. 14 shows calculated equilibrium charge fractions as a function of
ion energy [215]. These fractions are useful for the analytical calculations of electronic
stopping powers [216].
Cross Sections for Dressed Ions
The total ionization cross section for neutral hydrogen impact was obtained by a least-
square tting the experimental data of Bolorizadeh and Rudd [217]. Assuming similarity
with proton impact ionization, cross sections were approximated by scaling proton ion-
ization to give smooth transitions for the energy regions <20 or >150 keV/u, taking into
account the reproducibility of electronic stopping powers. Total ionization cross sections
for He
+
were tted to the experimental data of Rudd et al. [213] and Toburen et al. [200].
Total ionization cross sections for He
0
at energies lower than 100 keV/u were adjusted to
t the electronic stopping powers tabulated in ICRU Report 49 [203]. In the region below
30 keV/u, the stopping powers for He
0
is the main contributor. At energies above 100 keV/u,
the total cross sections were assumed to be the same as those of He
+
. Fig. 15 shows the total
ionization cross sections for H
0
, He
+
, and He
0
.
Figure 13 Charge exchange cross sections due to H
+
and H
0
(upper left panel), He
2+
(lower left
panel), He
+
(lower right panel), and He
0
(upper right panel) impact on water vapor. The curves are
tted to experimental data [199,211215] by various model functions and extrapolated where data
are lacking.
Figure 15 Total ionization cross sections due to dressed ion impact on water vapor. Cross sections
for H
0
and He
0
were adjusted to reproduce stopping powers for the lower energy protons and alpha
particles. (Experimental data from Refs. 200, 213, and 217.)
Figure 14 Equilibrium charge fractions of hydrogen beam (left panel) and helium beam (right
panel) in H
2
O calculated by the theory of Allison [215].
It was assumed that the spectra and angular distributions of electrons ejected from
the target molecule by neutral hydrogen impact were equal to that for protons. Toburen et
al. [200] have provided the ratios of SDCSs for ionization of water vapor by He
+
to those
for He
2+
as a function of the ejected electron energy. This ratio is distributed linearly from
0.4 to 1 for 0<e<90 eV for various projectile energies between 200 and 500 keV/u. The
energy spectra for secondary electrons because of He
+
impact were obtained by modifying
the Rudds model [Eqs. (18) and (19)] using a simple function g(e) such that:
dr
He
i
e
de
ge
dr
i
e
de
20
in which
ge 0:4 e=150 for e < 90 eV
1 for e z 90 eV
21
Fig. 12 (right) shows a good agreement between the calculated spectra and the experimental
data for He
+
energies of 200 and 500 keV/u. Available experimental angular distributions of
electrons ejected from water by He
+
are limited. To cover the broad ion energy range,
available proton data were used assuming that dierences of angular distributions between
dierent ions are not very large. Again, we assumed the spectra and angular distributions of
electrons ejected from the target molecule by He
0
impact to be equal to that for He
+
. We
assumed both excitation cross sections for protons [Eq. (15)] and elastic scattering cross
Figure 16 Mean lineal energy for 1 MeV proton tracks (left panel) and 5 MeV alpha particle tracks
(right panel) passing through and near a 1-Am diameter site. (), present calculations; () pits.
(From Ref. 74.)
sections for bare ions [Eqs. (16) and (17)] can be applied to respective cross sections for three
dressed ions (H
0
, He
+
, and He
0
).
Monte Carlo Codes for Low-Energy Ions
Based on the evaluated cross sections, a new generation of Monte Carlo track structure
codes were developed for simulation of tracks of low energy protons (the code lephist)
[175] and alpha-particles (the code leahist) [218] in water. The eective energy ranges are 1
keV1 MeV for protons and 1 keV8 MeV for alpha particles. The tracks of secondary
electrons were generated using the electron track code kurbuc. The codes can be operated
to generate tracks both in the track segment and the full-slowing-down modes. Tracks
were analyzed to provide conrmation on the reliability of the code and information on
physical quantities, such as range, W values, restricted stopping power, and radial dose
proles.
Model Calculation
Tissue equivalent proportional counter (TEPC) is the instrument for measuring the dis-
tributions of energy deposited in a specic volume. The instrument is commonly designed as
a spherical or a cylindrical volume with varying sensitive volume. Fig. 16 shows the dis-
tribution of mean lineal energy as a function of impact parameter b normalized by the radius
of the sensitive volume. The parameter b (the eccentricity) is the distance from the center of
the cavity to the chord of the ion cutting the sphere and R
sv
is the radius of the counter.
Distribution of the mean lineal energy were simulated for 1 MeV protons and 5 MeV alpha
particles through a wall-less counter of 1-Am diameter.
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18
Microdosimetry and Its Medical Applications
Marco Zaider
Memorial Sloan-Kettering Cancer Center, New York, New York, U.S.A.
John F. Dicello
Johns Hopkins University School of Medicine, Baltimore, Maryland, U.S.A.
1. INTRODUCTION
The quantity absorbed dose is used in medical physics on the assumption that when its
value is the same, irradiation of equal objects results in equal biological eects. In reality,
most of the biological eects of radiation depend on the microscopical pattern of energy
deposition and the absorbed dose is only the expected value (average) of the energy
deposited per unit mass. That the same dose of radiation may result in dierent eects,
when delivered by dierent types of radiation, is well documented. For instance, at low
doses, the relative biological eectiveness (RBE) of neutrons relative to g-rays to induce a
cell to become malignant is on the order of 100, which means that the ratio of absorbed
doses of g-rays and neutrons causing equal eects is about 100 [113].
The invention of microdosimetry some 50 years ago is a direct result of the
empirical observation that radiations have RBE p 1. This was unexpected because, on rst
principles, one would anticipate that biological eects would be proportional to the
(average) number of biomolecular disruptions produced by radiation in the sensitive sites
of the cell. On the other hand, all radiations act on biomatter primarily through the agency
of ionizations and excitations (presumably, the events that initiate biological damage).
Over a fairly large range of energies, the average energy expended to produce an ion pair
(
f
34 eV) is the same for all radiations. Thus, one expects proportionality between average
eect (E) and the average number of, say, ionizations in the cell:
Effect / z 1
In this expression, z, termed specic energy, is the energy imparted per unit mass to a
volume V; the expected value of z (see below) is the absorbed dose D. It follows that, on
average:
Effect / z D 2
which means that RBE=1. Conversely, RBE p 1 entails a nonlinear relationship between
eect and specic energy. For instance, if:
Effect / z
2
3
then:
Effect / z
2
p z
2
D
2
4
This means that in order to obtain a physical predictor of biological eect, one needs infor-
mation on the distribution f(z) of specic energy z. It also meansand this is the essential
pointthat the spatial pattern of energy deposition, which will change from one radiation
to another and thus account for dierences in f(z) among radiations, is an important pre-
dictor of biological eect.
The application of microdosimetry to medical physics derives from biological models
of radiation action (primarily, the Theory of Dual Radiation Action [14]) that explicitly
utilize for their predictions a microdosimetric description of the radiation eld.
Specically, they concern the following two problems:
(a) The RBE of a radiation eld with respect to conventional treatment modalities
(photon or high-energy electrons) for which extensive empirical data already exist.
This includes, as particular cases, RBE variations within the treatment eld as well
as brachytherapy, where low-energy photons (with RBE p 1) are frequently used.
(b) Predicting eect modications due to the temporal pattern of dose delivery.
We shall start with denitions of the principal microdosimetric quantities.
2. MICRODOSIMETRIC QUANTITIES
The basic concept of microdosimetry is the microdosimetric event (or, simply, event), which
is energy deposition by a charged particle and its statistically correlated particles (e.g.,
secondary electrons from the same particle track) [1517]. Events are important because
they are statistically independent entities. The principal microdosimetric quantity, specic
energy z, is dened as follows:
z
e
m
5
where e is the energy imparted by ionizing radiation to matter of mass m. The absorbed
dose D is the average energy imparted, per unit mass, by ionizing radiation. Formally:
D~r lim
V!0; ~roV
z 6
where z is the average specic energy in a domain of volume V centered at ~r, and the limit is
taken at constant density q.
A second quantity (physically equivalent to specic energy) is the lineal energy,
which is the quotient of e by l , where l is the mean chord length in that volume:
y
e
l
7
In this denition, e refers to energy deposition imparted in a single event, a restriction that
does not apply to z.
In the matter of mass density q, the relationship between z (in a single event) and y is:
z
4y
qS
8
This follows from a theorem by Cauchy [18] according to which the mean chord length l in
a convex site is given by 4V/S, where V and S are, respectively, the volume and surface
area of the site. For a spherical site of diameter d:
l
2
3
d 9
and thus:
z
4y
p d
2
q
10
which, for q=1 g/cm
3
and with units as indicated, becomes:
z
Gy

0:204
d
Am
_ _
2
y
keV=Am
11
The probability that the lineal energy delivered in single events is in the interval [ y,y+dy]
is denoted as f( y)dy. The corresponding distribution in z is f
1
(z)dz, where the subscript
makes explicit the fact that this distribution refers to single events only. The distributions
f(z), f
1
(z), and f( y) depend on the geometry of the site where specic energy is determined.
Two moments of these distributions that are often invoked are the frequency average y
F
(or z
F
) and the dose average y
D
(or z
D
). They are dened as follows:
y
F

_
l
0
yfydy; z
F

_
l
0
zf
1
dz
z
D

1
y
F
_
l
0
y
2
fydy; z
D

1
z
F
_
l
0
z
2
f
1
zdz
12
The rst and second moments of the multievent distribution f(z;n) are denoted z and z
2
,
respectively. Because, by denition, D z , the average number of events n at dose D is:
n
D
z
F
13
At a given dose D, the distribution f(z;n) [or, equivalently, f(z;D)] is determined uniquely
by f
1
(z). This can be understood from the following argument: By denition, the
probability of exactly m events is given by the Poisson distribution:
pm; n e
n
n
m
m!
14
If we denote by f
m
(z) the distribution of z in exactly m events, then f
m
(z) can be evaluated by
successive convolutions because, by denition, events are statistically independent:
f
0
z dz
f
1
z u f
1
z
f
2
z
_
l
0
f
1
zVf
1
z zVdzV
.
.
.
f
m
z
_
l
0
f
1
zVf
m1
z zVdzV
15
The distribution f(z;n) becomes:
fz; n
l
m0
pm; n f
m
z 16
which proves that if f
1
(z) is known, one can calculate f(z;n) for any value of n (i.e., D). One
can also demonstrate a general relationship between the moments of f(z;n) and f
1
(z) [17],
namely:
m
k1

M
k1
n

k1
j0
C
j
k
M
kj
m
j1
; k 0; 1; 2; . . . 17
Here, m
k
is the kth moment of f
1
(z) and M
k
is the kth moment of f(z;n) and:
C
j
k

kk 1 . . . k j 1
j!
18
With the notations used above (Eq. (12)):
z
F
m
1
; z
D
m
2
=m
1
19
In particular:
M
1
z nz
F
20
M
2
zz z
D
21
or, equivalently:
M
2
z
D
DD
2
22
an expression that provides the mathematical justication for the much used (and abused)
linearquadratic expression (see below).
The dose-averaged specic energy z
D
plays a fundamental role in microdosimetric-
based models of radiation action. For instance, it will be shown below that its magnitude
relative to D determines the extent to which doserate eects are important. If the micro-
dosimetric spectrum f
1
(z) is known, z
D
can be obtained by straightforward integration.
There is, however, a second more powerful procedure for obtaining this quantity and this
will be now explained.
z
D
depends on two elements: the structure of the charged particles tracks in the
radiation eld, and the geometry of the site where z is determined. One may adopt the
point of view that f
1
(z) obtains from the random overlap of two objects: the particle
track (represented as a collection of local energy depositions, ionizations, and excitations)
and the site of interest. Consider then two objects (three-dimensional domains) of volumes
V
1
and V
2
and let v represent the volume of their overlap when they are placed randomly
in space. One can show [19] that the rst two moments of v, E(v) and E(v
2
) satisfy:
Ev
2
Ev
V
1
V
2
_
p
1
rp
2
r
4pr
2
dr 23
where p
1
is the point-pair distribution of distances (ppdd) between pairs of points randomly
chosen in V
1
(and similarly for p
2
). This result is remarkable because it shows that the ratio
of the second to the rst moments of v can be factorized in functions (ppdd) that characterize
each object individually. This result can be immediately translated to microdosimetry [20].
Assume that in a charged particle track, the volume occupied by each transfer point
(ionization or excitation) equals the energy locally deposited. The overlap volume becomes
the energy e deposited in the site (V
2
), V
1
becomes the total energy T in the track, and V
2
is
the site volume. With this:
Ee
2
Ee
TV
2
_
p
track
rp
site
r
4pr
2
dr 24
The product between the ppdd and the volume of the site is termed the proximity function of
that domain. Thus, we have a proximity function of energy deposition:
tr track energy p
track
r 25
and the proximity function of the site:
sr site volume p
site
r 26
It is immediately recognized that:
z
D

1
m
_
trsr
4pr
2
dr 27
where m is the mass contained in the site. A few examples will illustrate the concept of
proximity function. For an object that occupies the entire space:
tr 4pr
2
28
For a track represented by a straight line of innite length:
tr 2 29
For a track of nite length L:
tr 2 1
r
L
_ _
r 2 0; L 30
For a spherical site of diameter d:
tr 4pr
2
1
3r
2d

r
3
2d
3
_ _
r 2 0; d 31
For other regular volumes, see Ref. 21.
In summary, microdosimetry is the study and quantication of the spatial and
temporal distributions of absorbed energy in irradiated matter [15,17,22,23]. One makes a
distinction between regional microdosimetry [the object of which is the study of micro-
dosimetric distributions f(z)] and structural microdosimetry (a mathematically more
advanced approach, which is concerned with characterizing the spatial distribution of
individual energy deposition events, i.e., ionizations and/or excitations). Regional micro-
dosimetry asserts that the eect is entirely determined by the amount of specic energy
deposited in the relevant site (typically, a cell nucleus). The two kinds of microdosim-
etry, regional and structural, were shown to be in fact mathematically equivalentonce
the sensitive site is judiciously determined [16].
3. RADIOBIOLOGICAL CONSIDERATIONS
3.1. The Theory of Dual Radiation Action
In order to obtain a quantity that relates to biological eect, one must postulate a functional
dependence of eect probability on specic energy. One such approach, the Theory of Dual
Radiation Action, takes as starting point the empirical observation that for numerous
eects, the yield of lesions (alterations responsible for the endpoint observed) depends
quadratically on specic energy [14]:
Ez bz
2
32
where b is a positive constant found to be only weakly dependent on radiation quality. The
form of this equation obtains by postulating that a lesion is the result of two molecular
sublesions, produced each at a rate proportional to z. On average:
ED bz
2
bz
D
DD
2
33
The last step follows fromEq. (22). The expression, Eq. (33), is the familiar linearquadratic
equation. In a more familiar notation:
ED aDbD
2
34
Thus:
z
D

a
b
35
Although not strictly valid, it is possible to extend this formulation to the probability of
cellular survival [reproductive inactivation S(D)] by making the assumptions that (1) one
lesion inactivates the cell, and (2) the number of lesions produced is Poisson-distributed.
When valid (mostly for low-LET radiation), it leads to:
SD e
aDbD
2
36
Examples of sublesions are single chromosome breaks that combine to produce a dicentric
aberration or single-strand DNA breaks, which, when in close proximity, result in double-
stranded DNA breaks. The expression, Eq. (35), provides the link between the micro-
dosimetric quantity z
D
, and the doseeect coecients a and b.
3.2. RBE
Within the linearquadratic formulation, the RBE of radiation H (a
H,
b
H
) relative to
radiation L (a
L,
b
L
) is given by [9,24,25]:
RBED
H

a
L
2b
L
D
H
1
4b
L
a
H
D
H
b
H
D
2
H
a
2
L
1
_ _
37
Note that the RBE is a decreasing function of D
H
. If b
H
gb
L
, and taking Eq. (35) into
account, one obtains the simplied expression:
RBE
1
2D
H
z
2
D;L
4D
H
z
2
D;H
D
H
_
z
D;L
_ _
38
If, furthermore, b
H
=b
L
c0, the RBE is independent of dose:
RBE
a
H
a
L
c
z
D;H
z
D;L
y
D;H
y
D;L
39
The ecacy of radiotherapy is generally considered to depend on the probability of cell
killing, 1S(D). Because RBE depends nonlinearly on absorbed dose, both the absorbed
dose and (through z
D
) the microdosimetric properties of the radiation eld must be known
at locations in the tumor and in the surrounding healthy tissues.
3.3. Temporal Effects
The temporal pattern of dose delivery, an important parameter in radiotherapy, further
changes the expressions derived thus far. To reinforce these ideas, consider the archetypical
lesion, a chromosomal dicentric aberration that obtains when two single chromosome
breaks (sublesions) misjoin. A pair of sublesions can be produced by a single track (single
event) or by two independent tracks. The yield of lesions that result via the rst mechanism
(termed intratrack action) is proportional to dose because the number of events is propor-
tional to dose. In contrast, and for analogous reasons, the second mechanism (intertrack
action) generates lesions at a rate proportional to D
2
. The two mechanisms are represented
in Eq. (34) by the linear (aD) and quadratic (bD
2
) terms, respectively.
An important consequence of this interpretation is the fact that the magnitude of the
quadratic term (but not the linear one) depends on dose rate. Indeed, in most cases,
sublesions undergo repair and thus the lower the dose rate [i.e., the larger the (average)
time interval that separates the formation of the two sublesions, the lower the yield of
intertrack lesions]. With this, the linearquadratic equation becomes:
ED aDbqtD
2
40
where q(t) is a functiontermed doserate factorthat modies the quadratic term to
account for the temporal distribution of dose.
Mathematical expressions for the function q(t) can be obtained for practically any
temporal pattern of dose delivery. It is commonly assumed that during the time interval, t
repair eliminates sublesion damage according to exp(t/t
0
), where t
0
is a characteristic
time required for repair (typically on the order of 1 hr). For instance [17]:
(a) For irradiations at a constant dose rate:
qr
2
r

2
r
2
1e
r
41
where r=t/t
0
. In particular, when t>>t
0
:
qi
2t
0
t
42
(b) For f well-separated fractions (complete sublesion repair in between fractions):
q
1
f
43
In a typical low-dose rate (LDR) treatment in brachytherapy, the total irradiation time is
on the order of several days and therefore qc0. It follows that the probability of cell
survival S(D), is quasi-exponential and the RBE is determined by the linear (a) coecient,
or, in microdosimetric terms, by z
D
.
(c) If the dose rate is decreasing exponentially (e.g., a temporary or permanent implant
with radioactive seeds), then [26,27]:
qt
2 kt
2
lt
2
1 k
2
=l
2
_ _
1 e
kt

2
e
klt
lt
1 e
2kt
2kt
_ _
1 e
2kt
2
_ _
44
Here l = log(2)/t
0
. At any given time t after the implantation, the absorbed dose D(t) is:
Dt
R
0
k
1 e
kt
_
45
where R
0
is the initial dose rate and k is the radioactive decay constant of the radioisotope
used.
(d) In the most general case [28]:
q
n
i1
a
2
i
t
0
c
i
t
0
e
c
i
=t
0
1
_ _ _ _
n
i1
n
ji1
a
i
a
j
t
2
0
e
b
j
b
i
=t
0
e
c
j
=2t
0
e
c
j
=2t
0
_ _
e
c
i
=2t
0
e
c
i
=2t
0
_ _
1
2
n
i1
a
2
i
c
2
i

n
i1
n
ji1
a
i
a
j
c
i
c
j
46
This is the dose rate factor for any arbitrary doserate distribution that consists of n con-
tiguous segments, and where a
i
, b
i
, and c
i
are, respectively, the dose rate, the center, and the
time required to deliver the doserate segment i.
3.4. Microdosimetric Constraints on Models of Radiation Action
An Upper Boundary for Eect as a Function of Dose
If each cell responds to radiation autonomously (i.e., independently of any other cell), an
upper limit of eect probability E(D) is the probability that at least one energy deposition
event actually occurred in it. This latter is given [by Poisson statistics, see Eqs. (13) and
(14)] by 1exp(D/z
F
) and thus, for any dose, one must have:
ED V1 e
D=z
F
SD u 1 ED z e
D=z
F
47
where S(D) is the survival probabilitymeaning here absence of eect. It is obvious
that at suciently large doses the linearquadratic expression, S(D) = exp(aDbD
2
)
does not satisfy this condition and thusas a matter of principle and independent of any
biological assumptioncan not be valid.
Denition of Low Dose and Low-Dose Rate
Microdosimetry provides an unambiguous denition of physical low dose, namely a dose
such that n = D/z
F
1. Indeed, under these conditions, each cell is essentially traversed by at
most one particle. Furthermore:
fz; Dce
n
dz e
n
nf
1
z 48
For any arbitrary expression e(z) describing the probability of eect as a function of z, one
has:
ED
_
ezfz; DdzcD
_
ez
z
F
f
1
zdz 49
which shows that at physical lowdoses, the eect probability E(D) must be a linear function
of dose irrespective of any specic biological mechanism. The expression, Eq. (49), is often
used in the form [29]:
ED D
_
Qz f
1
zdz 50
where Q(z) is taken as an empirical response function, the shape of which is obtained by
solving the system of integral equations:
E
i
D D
_
Qz f
1;i
zdz i 1; 2; . . . 51
where E
i
(D) is empirical (measured) probability of eect produced by radiation i with single-
event microdosimetric spectrum f
1,i
(z) [30,31].
A further consequence is thatwith no more than one event involvedeects must
be independent of dose rate if the cells respond autonomously.
In most situations, only a small fraction of events traversing the cell is causative. For
instance, only one 1 of 6000 electrons traversing a cell nucleus will produce a lethal lesion
[32]. A possibly more meaningful denition of low dose (biological low dose) can be
made in terms of these causative events (hits) by asking that the contribution of the
quadratic term in dose (bD
2
) be less than a certain fraction, say 10%, of the total eect.
Let D be this limiting dose. By denition:
bD
2
0:1aD bqD
2
52
When cells are irradiated at a constant dose rate Dover a time t, q is given by Eq. (45) and
this expression becomes:
1
1
18Dt
0
a
b
_ _

Dt
0
D
1 e
D=Dt
0
_ _
53
Note that this is an equation for D as a function of a/b, both in units of Dt
0
. For tumor cells
(a/b = 10 Gy, t
0
= 0.5 hr, D = 2 Gy/min), q c1 and D = 1.1 Gy, which is signicantly
larger than the physical low-dose limit of 2 mGy. Note that D is an upper limit for the doses
where Eq. (53) is valid.
The KellererHug Theorem
This theorem, given here without demonstration, sets up a lower limit for the mean
number of inactivating events m. Given a probability of eect E(D) or its complement
S(D) = 1E(D), dene the mean inactivation dose [33]:
d
_
SDdD 54
and its variance:
r
2
2
_
DSDdDd
2
55
The mathematical statement of this theorem is:
m z
d
2
r
2
56
The mean number of inactivating events is d/z
F
.
4. MICRODOSIMETRIC DISTRIBUTIONS: EXPERIMENTAL TECHNIQUES
The experimental techniques used in microdosimetry are quite complex, and a complete
description is beyond the scope of this chapter (see Ref. 17). Conventional experimental
techniques do not provide methods for measuring frequency distributions of energy
depositions in sites with dimensions in the micrometer range or smaller, and a number
of alternate methods that are capable of providing equivalent information for many
biomedical applications have been developed. The underlying concept for most of these
methods is as follows: The mean energy imparted by a particle traversing a thickness x of
specied material of density q depends only on x and q. One can obtain equal energy
depositions by manipulating x and q such that their product xq remains constant. Thus, a
microscopical volume (x
f
1 Am, q =1 g/cm
3
) can be simulated with a larger cavity (x a few
centimeters) by correspondingly reducing the density. For instance, a 2.5-cm diameter
sphere lled with a propane-based tissue-equivalent (TE) gas at 17 Torr is equivalent to a
1-Am diameter of unit density tissue. In practice, it is usually not possible to exactly match
the atomic compositions of the gas and the solid. A typical counter consists of a spherical
or cylindrical cavity (called sensitive volume) lled with gas and delimited by a solid wall
material, and a central wire placed along the counter diameter and isolated electrically from
the counter wall. The traversal of the counter by charged particles results in the production
of ion pairs. If a voltage is applied between the (conductive) wall and the central wire, the
ions will drift along the electrical eld and induce an electrical signal at the collecting elec-
trode. The amount of charge collected is a measure of the energy deposited in the counter.
Figure 1 Schematic diagram of the Rossi proportional counter (see text for details).
For x-rays or g-rays, the average signal thus obtained is very weak relative to background,
and typically one runs the detector in the so-called proportional mode. This is achieved by
setting a suciently large voltage for the drifting ions to acquire enough energy to produce
second-generation and higher-generation ions through collisions with gas molecules. A
schematic diagram of a typical detector, usually called a Rossi proportional counter in ref-
erence to H. H. Rossi whose group pioneered this eld, is shown in Fig. 1.
5. MICRODOSIMETRIC DISTRIBUTIONS: THEORETICAL METHODS
For various technical reasons [17], the empirical determination of microdosimetric spectra
is not always possible, particularly for site sizes signicantly smaller than 1 Am or for
volumes of irregular shape. In these situations, calculations may be used instead. A key
element facilitating this approach is the possibility of regarding the spectrum of energy
deposition as resulting from the random overlapping of two objects: the charged-par-
ticle track (essentially, a collection of energy transfer points), and the sensitive site [14,15,
22,23,34]. Theoretical microdosimetric distributions are generated by randomly placing a
site on a Monte Carlo-generated track. In a sense, this is the opposite of what happens
in an experiment where the detector (a xed object) is traversed by random tracks. To the
extent that accurate cross sections for the interaction of the ionizing particles with the
medium are known and the code can adequately simulate the spatial and structural geo-
metries, theoretical calculations potentially represent the best procedure for obtaining mi-
crodosimetric quantities.
A full description of computational techniques in microdosimetry is beyond the
charter of this chapter and the interested reader may consult the textbook by Rossi and
Zaider [17]. Briey, the calculation proceeds along the following lines:
For a given source, one generates at each point in space the electron distribution in
energy (slowing down spectrum) n(E); commercially available codes are available for this
purpose.
For each electron energy E, the interactions with tissue (frequently represented by
liquid water) are simulated event by event, which means that one obtains a detailed
description of the geometrical coordinates, energy locally deposited, and type of energy
transfer (ionization or excitation) for each interaction point, primary or secondary.
Microdosimetric spectra f( y;E) for events transferring energy E are generated by ran-
domly placing the volume of interest (commonly, spheres or cylinders) on each track and
then evaluating, at each instance, the total energy deposited in it.
The lineal energy spectrum of the brachytherapy source is evaluated from:
fy
_
l
0
nEE
y
F
E
fy; EdE
_
l
0
nEE
y
F
E
dE
57
6. MICRODOSIMETRIC DISTRIBUTIONS FOR RADIATIONS USED
IN RADIOTHERAPY
6.1. Brachytherapy
Brachytherapy physics is concerned with electrons, whether primary or secondary, as in
the case of photon sources (Table 1).
At low doses or low-dose rates, the RBE of 100 keV photons relative to, for example,
1-MeV photons may exceed 2 [35,36]. For instance, the RBE for
125
I has been extensively
studied and results of 1.22 have been reported for the doserate range of 0.039 Gy/hr
[37]. Similarly, for
103
Pd, a study performed at 0.070.8 Gy/hr reported RBE values of
1.9F0.7 [3740]. While considerably lower RBE values apply to the higher doses or dose
rates usually employed in external radiotherapy, dierences in biological eectiveness on
the order of 1015% remain.
Microdosimetric distributions have been determined for a wide range of photon
energies, including those of the photon sources quoted in Table 1. Kliauga and Dvorak
[41] measured lineal energy spectra for photon energies in the range 121250 keV and for
site diameters of 0.247.7 Am. Fig. 2 shows these spectra as a function of photon energy.
Microdosimetric distributions for
103
Pd-,
125
I-,
241
Am-, and
192
Ir-encapsulated
sources were published by Wuu et al. [36] and are shown in Fig. 3. Table 2 gives y
D
and RBE values for some of the distributions shown in Fig. 3.
These spectra have notable common characteristics. All the spectra have a modal en-
ergy deposition that is related to the average energy lost per unit path length by the primary
particles. Because the lower energy electrons have a higher mean dE/dx, the spectra for the
lower energy photons and electrons tend to peak at the higher lineal energies. Conversely,
the higher energy particles have peaks at lower lineal energies. There is a decreasing
probability of events at lower lineal energies characteristic of the frequency distribution
of ionizations associated with the production of a single electron with energy close to zero
(i.e., an energy deposition just sucient to produce an ion pair). Irrespective of the mean
energy deposited, there is a kinematic upper limit, which represents secondary electrons with
precisely enough energy to make it across the diameter, thus depositing their total energies in
the sensitive volume. Electrons of lower kinetic energy must deposit less total energy, and
higher energy electrons will deposit only a fraction of their energy with a lower dE/dx.
6.2. High-Energy Electrons, X-Rays, and gg-Rays External Beam Therapy
Particles emitted from radioactive isotopes are generally too low in energy to provide the
penetration required for conventional treatments of tumors with external radiation beams.
Most external beam radiation therapies are performed with high-energy x-rays or
electrons produced with compact linear accelerators with accelerating potentials between
about 4 and 20 MeV. One notable exception is certain devices designed for stereotactical
radiosurgery or radiation therapy of supercial tumors that use cobalt-60 g-rays. The
Table 1 Physical Characteristics of Radioactive Sources Currently Used
in Brachytherapy
E
c
[MeV] E
b
(max) [MeV] T
1/2
137
Cs 0.662 1.17 30. years
198
Au 0.416 0.96 2.7 days
192
Ir 0.380 0.67 74.2 days
125
I 0.028 60.2 days
103
Pd 0.021 17. days
131
I 0.364 0.61 8.06 days
90
Sr/
90
Y 2.27 28.9 years
32
P 1.71 14.3 days
106
Ru/
106
Rh 3.55 367. days
Figure 2 Microdosimetric distributions for photons of dierent energies. (From Ref. 41.) The
spectra were measured in a 1-Am diameter spherical cavity.
Figure 3 Microdosimetric distributions for several photon radiations commonly used in
brachytherapy. (From Ref. 36.)
higher average energy of these therapy beams provides reduced attenuation and, therefore,
more dose at depth. At the same time, this results in events of lower average lineal energy,
as shown in Fig. 4 [42].
6.3. Heavy Particles in Medicine
It was quickly recognized after the development of high-energy particle accelerators that
accelerator-produced particles provided better penetration and more dose to the treatment
Table 2 Dose-Averaged Lineal Energy for the
Distributions Shown in Fig. 3
Radionuclide y
D
[keV/Am] RBE
103
Pd 3.8 2.3
125
I 3.5 2.1
241
Am 3.5 2.1
192
Ir 2.0 1.3
60
Co 1.6 1.0
Figure 4 Microdosimetric distributions as a function of lineal energy in a 2-Am equivalent
spherical detector. The solid line is a spectrum for cobalt-60 g-rays, and the dashed and dotted lines
are the spectra for 10- and 15-MeV bremsstrahlung x-rays.
volume while sparing the surrounding normal tissues. In addition, dierent particle types
produced dierent biological responses in both the malignant and normal tissues. This led
research groups to speculate that particles other than photons or electrons might have
physical and/or biological advantages in comparison. Clinical trials have taken place using
proton beams, neutrons, energetic heavy ions, and even negative pions. The protons,
pions, and heavy ions, in contrast to the exponential attenuation associated with electrons
and photons, have a relatively constant dE/dx with depth until near the end of their range,
where there is a rapid increase in energy deposited, reaching a maximum at what is called
the Bragg peak and followed by a rapid decrease. This type of depthdose curve is better
suited to deposit more dose in the treatment volume while sparing the surrounding normal
tissues. Negative pions have the added characteristic that, at the end of their range, they
disintegrate, transforming most of their rest mass (about 140 MeV equivalent) into sec-
ondary radiations. This is literally a localized submicroscopical nuclear explosion. Today,
protons and, to a lesser extent, energetic heavy ions are being used routinely to treat cancer
patients in a limited number of facilities. Although such particles showed that dose local-
ization can be a major advantage for specic diseases, their higher costs in relation to
electron accelerators [43] have restricted their use to a few centers, instead stimulating the
development of improved technologies with photons to achieve increasingly better dose
distributions at, unfortunately, increasing costs.
Therapeutic beams of energetic protons and heavy ions result not only in a dierent
depth dose distribution but also in dierent microdosimetric spectra as well. Energies for
protons used for therapy are nearly minimum ionizing and their microdosimetric spectra
are similar in the range of lineal energy to that of higher-energy electrons and photons, as
seen in Fig. 5 [44]. For the same energy per nucleon, the average dE/dx of the particles
increases with increasing atomic mass, with a corresponding increase in the linear energies,
as seen in Fig. 6 [45].
Figure 5 Microdosimetric spectra at the proximal, central, and distal positions of a therapeutic
proton beam with an initial energy of 155 MeV.
Moreover, for monoenergetic heavy ions of the same energy per nucleon, the average
number of ion pairs increases with a corresponding decrease in the deviation about the
mean, so we have a higher modal value with a more sharply dened Bragg peak.
The previous theoretical discussion tells us that increasing ionization density, such as
that observed with increasing ion mass, could result in a higher biological eectiveness, at
least until saturation sets in. Saturation in this case refers to large energy depositions that
have such a high probability of producing the biological endpoint that increased energy
deposited has little, if any, increased eect. We might expect, then, that changing the particle
type and energy might change the relative biological eectiveness of the particle compared
with photons and, therefore, the clinical outcome. This is indeed the case, rendering the RBE
a clinically useful parameter to vary, with the expectation that particles with higher RBEs
might be more eective in eradicating tumor cells. This is in part the motivation for the use of
beams of energetic heavy ions.
Unfortunately, energetic heavy ions require expensive, large accelerators to produce.
If increased biological eectiveness were the main therapeutic benet, with improved dose
localization not a major issue, then neutron beams might be more desirable. Fig. 7 shows
microdosimetric spectra for neutron beams as a function of the nominal neutron energy.
Experiments generally show that energetic neutrons are at least as eective as most
heavy ions for producing most biological eects. Although they are generally no better than
photons in terms of dose localization, they are much less expensive to produce. Therefore, if
biological eectiveness is the main clinical requirement and dose localization is not im-
portant, then neutron beams may be the modality of choice. Neutrons have been the focus of
clinical investigations for at least six decades, and today they are used for conventional
Figure 6 Microdosimetric spectra for various heavy ion beams as noted with nominal energies of
approximately 600 MeV per nucleon. Corresponding spectra for cobalt-60 g-rays, protons, and 14.5-
MeV neutrons are included for comparison.
external beam therapy in a few therapy centers. Clinical investigations of boron neutron
capture therapy are underway to take advantage of the increased RBEs with neutrons and,
and the same time, to conne the dose primarily to malignant cells. Lower-energy neutrons
have an exceptionally high interactioncross section with boron, so the boron is preferentially
loaded into cancerous cells via appropriately selected antibodies.
We had mentioned that negative pions have been used in clinical trials for cancer
therapy. They approach the dose localization of protons with an enhanced RBE in com-
parison with protons or photons. Because the pion mass is lighter than that of protons and
heavier ions, the scattering is greater and edges are less sharp. Moreover, although the
eectiveness of pions can be greater than that of protons or photons, it is generally lower
than that of neutrons or heavy ions. Finally, pions are produced as secondary particles at
higher energies and, therefore, are more expensive to produce at intensities suitable for
therapy. Although a few institutions have used pions in clinical trials with results com-
parable to those of neutrons and heavy ions, there are no such studies underway at this time.
In summary, the variety of radiation types available for both external beam radio-
therapy and brachytherapy provides multiple means of localizing the dose for maximum
eectiveness in specic applications. The variation in the microdosimetric spectra results in
corresponding variety in radiation quality and biological eectiveness, providing insight
into the mechanistic processes of energy transfer and dierent mechanisms for attacking
persistent diseases. Building upon this cadre of radiations, after a hundred years in the clinic,
radiation therapy remains one of the primary oncological methods for controlling cancer.
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19
Charged Particle and Photon-Induced
Reactions in Polymers
S. Tagawa, S. Seki, and T. Kozawa
SUMMARY
Basic and applied researches on charged particle and photon-induced reactions of polymers
are surveyed. The basic parts are fundamentals of radiation eects on polymers and pulse
radiolysis studies on polymers. The intermediate parts are a great diversity of radiation
eects on polymers and reaction mechanisms of electron beam (EB) and x-ray resists. The
applied parts are economic scale of utilization of radiation and industrial application of
radiation to polymers.
1. INTRODUCTION
Since the rst studies of radiation eects on polymeric materials, fundamental researches on
radiation-induced reactions in polymers have been widespread, and the eld of their
applications has been growing until now. Seeds of typical application of dierent types of
radiation were introduced by Chapiro and by Charlesby during the 1950s, and great deal of
work has been published in this eld concerning various polymeric materials and radiation
sources. This is due to quick or sensitive responses of macromolecules to radiation, because
few reactions can dramatically change such macroscopic properties of polymeric materials
as solubility, mechanical properties, and thermal stability. Cross-linking and chain-scission
reactions caused by irradiation have been treated as the key reactions controlling the
properties of macromolecules. Decision of the predominant reaction in a polymer for a
radiation source has been very important to predict the possibility of modication of the
polymer for engineering applications. This approach to the combination of radiation and
polymers has been practically useful because polymeric materials have been the leading
structural materials, so that polymers are now used in every stage of our daily life.
However, recent progress in both radiation and polymer researches indicates a
dramatic change in the circumstance of this research eld, and the trend has been rapidly
expanding, especiallyinthe last decade. Polymers will be usednot onlyas structural materials
but also as electronic, optical, medical, and pharmaceutical materials, and radiation will be a
powerful candidate to manipulate the structure andproperty of polymers. In this section, the
potentials of radiation and polymers are reviewed for the forecast of technology in the
twenty-rst century.
2. ECONOMIC SCALE OF UTILIZATION OF RADIATION
The economic scale of utilization of radiation has been surveyed several times by many
organizations. Mainly from the viewpoint of public acceptance (PA), Management Infor-
mation Services, Inc., in the United States conducted a survey to clarify the size of those
economic scale [1] and the results were presented by Alan E. Walter, the former president of
the American Nuclear Society, at conferences [2]. Similar studies were done in Japan, but the
data had poor consistency for comparison. To overcome this shortcoming, in 1999, the
Special Committee for Evaluation of Economy on Utilization of Radiation examined
the Japanese economic scale of utilization of radiation, consistently and systematically, for
the rst time, based on reliable published data and reasonable assumption both under the
sponsorship of the Ministry of Education, Culture, Sports, Science and Technology
(MEXT) and with the support of the Japan Atomic Energy Research Institute (JAERI).
The evaluation was based on economic indices indicating the magnitude of the market
created by products manufactured through use of radiation.
We performed a detailed comparison of the economic scale of radiation use in the
elds of industry [4], agriculture [5], and medicine [6] in Japan and the United States. The
comparison between Japan and the United States was also done for an economic index
regarding market creation of products obtained from use of both radiation and nuclear
energy [7]. The results of our study are compared for the year 1997.
The economic scale is compared between the United States and Japan with selected
industrial parameters such as sterilization, semiconductors, radiographic testing, and radial
tire production, because the very large industrial markets make a whole comparison
dicult. The economic scale revealed in selected industrial elds was about $56 billion for
the United States and $39 billion for Japan. The former is larger by a factor of
f
1.4 [4].
The economic scale of the application of radiation in the eld of agriculture in Japan
was estimated from public documents to be about $964 million in 1997. The economic scale
survey in food irradiation and mutation breeding was extended to the United States for a
direct comparison to the situation in Japan. The maximum estimation amounted to $3.2
billion for food irradiation and $11.2 billion for mutation breeding. The economic scale for
products in selected agricultural elds was $14.5 billion for the United States and about
$0.8 billion for Japan, implying that the former is larger in magnitude by a factor of about
18 [5].
The economic scale of the use of radiological technology in medicine in Japan in 1997
was about $10 billion. The economic scale in 1997 was compared between Japan and the
United States [6]. Within the same limited parameters, the economic scale of the use of
radiological technology in medicine was approximately $49 billion for the United States and
$12 billion for Japan. The former is larger in magnitude by a factor of 4, implying that
practitioners in the United States do not hesitate to use radiological technologies for medical
applications. This tendency was clearly observed by the expenditure on prostate cancer,
FDG-PET, and so on.
In 1997, the economic scale of radiation usage was estimated to be $119 billion (1.4%
of GDP) in the United States and $52 billion ($1 =121 yen) (1.2%of GDP) in Japan. In the
United States, the use of radiation technology not only in industry but also in medicine is
signicantly advanced. The usage in agriculture is relatively small compared to those in
industry and medicine both in the United States and Japan. Usage in the agricultural sector
in Japan is much smaller than in the United States [7].
3. RADIATION-INDUCED REACTIONS IN POLYMERS
3.1. Fundamentals of Radiation Effects on Polymers
Early processes caused by high-energy charged particles and photons have already been
described in other chapters. Some characteristic processes occurring in the polymeric
systems are focused on in the present chapter. It is well known that in some radiation
chemical processes, the energy consumption in the process is far smaller than the energy
deposited by incident radiation, indicating that most of the energy is consumed by radiative
and/or nonradiative decay of excited states via energy transfer processes instead of pro-
ducing reactive intermediates. One very important example of this is the so-called protection
eects of polyolen by addition of aromatic molecules [8]. Energy and charge transfer pro-
cesses are in relation to each other, and these are systematized theoretically in the condensed
phases including polymeric systems. It is because of the high mobility, hence, of the large
diusion constant of charged species even in the polymeric system. It provides a validity of
the formulation developed in the liquid or solid phases for extension to polymeric systems.
In contrast, diusion processes of neutral reactive intermediates strongly depend on the
structure, molecular mobility, dielectric constants, etc. of solid materials. Although the neu-
tral species including (free) radicals bear strict limitation in their migration they are very
important promoters of radiation-induced reaction in the polymeric systems.
Energy Transfer Process
Several dierent processes have been accounted for transfer of electronic excitation energy
between molecules or functional groups in macromolecules: (1) electron exchange inter-
action, (2) radiative excitation transfer, (3) excimer migration, (4) exciplex excitation
transfer, and (5) long-range excitation transfer. Electron exchange interaction occurs over
a very short distance via some overlap of molecular orbitals of the excitation donor and
acceptor, called a Dexter-type energy transfer process [9]. Only the limitation of this transfer
process is the conservation of the total spin of the system. Radiative transfer is due to the
reabsorption of emission from a donor molecule by an acceptor via a photon. It needs the
overlap between an acceptors optical absorption and emission spectrum of a donor. There
is no total spin conservation in the system; however, the triplet state of the acceptor is not
formed because direct transition is usually spin forbidden. Excimers and exciplexes are the
pairs of an excited molecule and an unexcited molecule [10], and the excimer is the pair
formed between two consistent molecules [10]. Excimer formation has been reported in
many systems of solids, liquids, and gases. One example of the excimer formation in
radiation chemical processes is the excimer of phenyl groups in polystyrene of which the
yield, absorption, kinetics, and emission have been precisely reported to date [11,12]. Long-
range excitation transfer is mainly caused by a Coulomb interaction between an excited and
an unexcited molecule that are making simultaneous coupled electronic transitions of
almost equal energy. This is the so-called Fo rster-type energy transfer (inductive resonance
or vibrational relaxation transfer) (for a review, see Ref. 13). The transfer occurs with a
relatively slow rate constant because the motive force of the transfer, namely, the dipole
dipole interaction (coupling) of molecules, is very small compared to the width of the
vibrational band of the excited state of the donor molecule. This leads to the transfer from
the lowest vibrational excited state of donor molecules after vibrational relaxation, but
enables long-range excitation transfer over
f
10 nm in a single step.
In the real polymeric system, a large number of modeling eorts have been made for
energy transfer processes caused by radiation as well as low-energy photons, and direct or
indirect observation of excited-state dynamics has also been performed for a variety of
polymeric systems. The earliest modeling work of excitation dynamics in polymeric systems
was given by Simpson for polyenes by treating them as the chained analogs of simple
molecules having k conjugation [14]. The developed modeling and experimental evidence is
noted later. To date, the formation of the excited states, the energy transfer, and decom-
positionfromexcitedstates inthe radiation chemical processes have been studiedover a wide
range of polymeric systems: hydrocarbon polymers without double bonds (polyethylene,
polypropylene, etc. [1519]), saturated polymers with aromatics (e.g., polystyrene, poly-a-
methylstyrene, polyvinylcarbazole [11,12,2022]), k-conjugated polymers (e.g., polypheny-
lenevinylene, polythiophene [2225]), and j-conjugated polymers (e.g., polysilane, poly-
germane [26,27]). LET and temperature eects on excited states of solid-state polystyrene
[28a,b] and solid-state polysilanes [28c] were studied by ion beam pulse radiolysis.
Radical Processes
When a polymeric system is exposed to high-energy radiation, the system undergoes main-
chain scission and the creation of cross-links, end-links, double bonds, free radicals, etc. The
neutral radicals are the key promoters of the reactions above, and the structure, reactivity
(stability), migration, etc., have been extensively investigated by many techniques including
ESR. Details of the techniques and their results are described in other chapters or reviews
(for a book, see Ref. 29), and the eects of the above reactions on polymeric systems are
mainly discussed in the present section.
On the basis of no dierence in the probability of main-chain scission in any part of
the polymer backbone (no chain end eect), an approach to the statistical treatment of
main-chain scission was given by Charlesby in 1954 [30]. Although main-chain scission is
directly related to the degradation of a polymeric system, cross-linking and end-linking
reactions cause more dynamic changes in its macroscopic behavior such as gelation of the
polymers, which have produced many industrial applications: radiation curing, stiening,
grafting, etc. It is also a reasonable assumption that cross-linking and end-linking reactions
are produced randomly by low-LET radiation and the number of links is proportional to
the radiation dose, so long as the number of cross-links is suciently small in comparison to
the total number of structural units. Classical statistical theory of main-chain scission and
cross-linking were given by Kuhn in 1930 for chain scission [31], by Flory for cross-linking
in 1941 [32], and modied by Charlesby in 1953 [33]. The initial formulation of main-chain
scission and cross-linking probability is given as CharlesbyPinner relationship by
1=M
n
1= M
n

0
p
0
0:5q
0
D=m 1
1=M
w
1= M
w

0
0:5p
0
q
0
D=m 2
where p
0
is the probability of scission and q
0
is the probability of cross-linking. M
n
and M
w
denote the number and weight average molecular weight with their initial values of (M
n
)
0
and (M
w
)
0
, respectively, m is the molecular weight of a unit monomer, and D (MGy) is
absorbed dose. Gvalues of main-chain scission and cross-linking are related to the values of
p
0
and q
0
as follows,
Gs 9:6 10
3
p
0
3
Gx 4:8 10
3
q
0
4
where G(x) is the Gvalue of cross-linking and G(s) is the Gvalue of main-chain scission. The
above statistical equations were superior for the ease of calculation to other classical
theories; however, they were not sucient to give an entire solution of main-chain scission
and cross-linking of a polymeric systembecause of the assumption of the theory of an initial
arbitrary molecular size. This gave some diculties regarding average molecular weight,
solubility, viscosity, etc. Problems with the molecular weight distribution and its change
with the irradiation were solved by Saito [34] and by Inokuti [35]. In their theory, molecular
weight distribution was expanded by the Poisson and/or SchulzZimm distributions, and
changes in the distribution by the simultaneous reactions of main-chain scission and cross-
linking were analytically traced. All of these initial works were done in parallel, and the
following work developed on the starting points so provided.
ODonnell et al. used a binominal expansion of the initial molecular weight distribu-
tion and discarded higher terms than a cubic factor [36]. This leads to a computer simulation
to trace the changes in the molecular weight of polymers without using a mathematical table.
In the 1990s, modied formulations of chain scission and cross-linking were proposed by
Zhang et al. [37] and Olejniczak et al. [38]. Sun introduced a parameter h, which was related
to the glass transition temperature of the polymer, and took the eects of molecular stiness
of the polymers into account. Rosiak proposed a deductive distribution function of
molecular weight on the basis of an arbitrary distribution and extended the validity of the
CharlesbyPinner relationship. Major diculties have been steadily solved by many
attempts to improve the formulation; however, some new problems have also arisen in
recent progress in the investigation of radiation-induced reactions in some polymeric
systems. Nowadays, approach to main-chain scission and cross-linking reactions still
contains some assumptions: (1) G(s) and G(x) are constant with radiation dose, (2)
occurrence of scission and cross-linking may be treated separately and independently, (3)
random scission and cross-linking occur in the system, (4) not more than one cross-link
connects any two polymer molecules, etc. Some of these assumptions have been revealed to
be incorrect in some polymeric systems and for high-LET radiation. The problems will be
discussed in the following sections.
3.2. Pulse Radiolysis Studies on Polymers
Recent pulse radiolysis studies on polymers [39,40] and monomers [41] are reviewed from
1990. Very high quality of pulse radiolysis systems is required for pulse radiolysis studies on
polymers and polymeric systems, especially polymer and polymeric intermediates, because
of the complexity of reactions and small absorption coecients of reactive intermediates of
both polymers and polymeric systems compared with the reactive intermediates of aromatic
molecules such as pyrene and biphenyl. Therefore, most of pulse radiolysis studies on
polymers are studies on reactive intermediates of solute molecules, such as pyrene in polymer
and polymeric systems. Recent progress in pulse radiolysis studies on polymers and poly-
meric systems has been enhanced mainly by the development of both pulse radiolysis tech-
niques and advanced technology such as lithography. The development of pulse radiolysis
techniques has beendone by improvement of electronbeamintensityandstability, sensitivity
and dynamic range of photodetectors, time resolution of pulse radiolysis, wavelength region
of monitor light, and experimental temperature. Especially, mention may be made of the
development of laser synchronized picosecond [42] and subpicosecond [43] pulse radiolysis
systems and the application of low-temperature nanosecond pulse radiolysis technique over
a wide range of temperature [44a] with the monitoring wavelength region from 300 to 1600
nm [44b] to polymers and polymeric systems. Details of the progress in laser synchronized
picosecond and subpicosecond pulse radiolysis are described in another chapter.
Polystyrene and Related Compounds
The radiation chemistry of polystyrene (PS) in solution has been studied by many groups.
Absorption peaks of the intramolecular excimers of PS at 530 nmand poly-a-methylstyrene
at 520 nm in p-dioxane solutions [45a], and absorption peaks of a charge transfer (CT)
complex between a polystyrene phenyl ring and Cl atom at 320 and about 500 nm in
chloroformsolutions [45b], were observed for the rst time by using laser ash photolysis in
1980. Later, the CTcomplex between poly-a-methylstyrene and Cl atom[45c] was observed.
Intermediate species of PS in solutions, such as the CTcomplex [21a] and the intramolecular
excimer [46], were studied by using pulse radiolysis. The lifetime of the excimer absorption
and uorescence of polystyrene is 20 nsec [21b,45a,46]. The intramolecular excimer
formation and energy migration of oligostyrenes [21c,21d] were studied by using pulse
radiolysis. The CT complex between a PS phenyl ring and a Cl atom was formed through a
geminate ion recombination [21a] whose kinetics was dierent from that between the CT
complex and the excimer. Lifetimes of the CT complexes in CCl
4
and CHCl
3
were about 200
and 420 nsec, respectively, dominated by hydrogen abstraction fromPS by Cl atom[21a,46].
In the pulse radiolysis study on polystyrene solution, only the tail of absorption band due to
polystyrene intramolecular dimer cation radical was observed in less than 1000 nm by
previous laser ash photolysis and pulse radiolysis of PS in both solution and solid lm
[21b].
Recently, by using improved nanosecond pulse radiolysis with the monitoring wave-
length region from 300 to 1600 nm [44], absorption spectra due to main reactive inter-
mediates such as the intramolecular dimer cation radical in the near-IR wavelength region
were clearly observed in the pulse radiolysis of polystyrene in various solutions [47]. For
example, Fig. 1 shows the absorption spectra observed in the pulse radiolysis of polystyrene
solutions in CH
2
Cl
2
.
Saturated Hydrocarbon Polymers
Absorption due to main intermediates such as polymer cation radicals and excited states,
electrons, and alkyl radicals of saturated hydrocarbon polymers had not been observed for a
long time by pulse radiolysis [39]. In 1989, absorption due to the main intermediates was
observed clearly in pulse radiolysis of saturated hydrocarbon polymer model compounds
except for electrons [39,48]. In 1989, the broad absorption bands due to polymer excited
states in the visible region and the tail parts of radical cation and electrons were observed in
pulse radiolysis of ethylenepropylene copolymers and the decay of the polymer radical
cations were clearly observed [49]. Recently, absorption band due to electrons in saturated
hydrocarbon polymer model compounds was observed clearly by pulse radiolysis [49] as
shown in Fig. 2. In addition, very broad absorption bands in the infrared region were
observed clearly in the pulse radiolysis of ethylenepropylene copolymers [50] as shown in
Fig. 3. Radiation protection eects [51] and detailed geminate ion recombination processes
[52] of model compounds were studied by nano-, pico-, and subpicosecond pulse radiolyses.
Polysilanes
Very intense and sharp near-UV absorption bands due to radical ions of polysilanes [53a,b]
and polygermanes [53c] were observed by nanosecond pulse radiolysis. Broad visible and IR
absorption spectra due to the radical ions of polysilyne [54] and polygermyne [54] were also
observed. Very systematic pulse radiolysis studies on many dierent kinds of polysilanes [55]
have been made by our improved nanosecond pulse radiolysis system over a wide range of
Figure 1 Transient absorption spectra obtained in the pulse radiolysis in 200 mM (base mM unit)
polystyrene solutions in CH
2
Cl
2
at the pulse end (
x
) and 100 nsec after the pulse (D). Inset: time-
dependent behavior observed at 1200 nm.
Figure 2 Transient absorption spectra obtained in the pulse radiolysis of neat n-dodecane.
temperature and with the monitoring wavelength region from 300 to 1600 nm [44]. Both
radical cations and anions of polysilanes have very intense sharp near-UV and very intense
and broad absorption bands as shown in Fig. 4 [55a]. Transient absorption spectra due to
excited states [26,27a,b] and radical cations [27c] of polysilanes were also observed by laser
ash photolysis. Detailed studies on radical ions of oligogermanes were performed by
nanosecond pulse radiolysis [56].
Poly(Methyl Methacrylate)
A broad, structureless absorption in the 350- to 500-nm region was observed in pulse
radiolysis of additive-free poly(methyl methacrylate) (PMMA) in 1969, but the assignment
of the absorption was not possible at that time [57]. Then absorption peaks at 725 and 440
nmwere ascribed to the radical anion and the radical cation of PMMA, respectively, in 1983
[58]. However, these assignments were not compatible with the results obtained in pulse
radiolysis of solutions of PMMA and its substituted analogues [59]. No distinct absorption
peak at 440 nm was observed and a short-lived absorption component around 440 nm was
attributed to PMMA radical anions [59]. For pulse-irradiated solid PMMA, no distinct
absorption peak around 440 nm was observed by the pulse radiolysis of solid PMMA with
0.1-Asec time resolution, from 320 to 620 nm, and the short-lived absorption component
around 440 nm was attributed to PMMA radical anions [60]. Transient absorption spectra
of irradiated additive-free solid PMMAcontaining MMAmonomers were clearly observed
by our improved nanosecond pulse radiolysis system over a wide range of temperature and
with the monitoring wavelength region from 300 to 1600 nm [44]. Absorption bands due to
PMMA radical anions and MMA dimer anions [61] were observed in the UV and near-IR
regions, respectively, as shown in Fig. 5.
3.3. Diversity of Radiation Effects on Polymers
Classical investigations of radiation eects on polymers have been summarized in some
books or reviewarticles in the 1970s to the 1990s [29,6264]. Many of the works were focused
Figure 3 Transient absorption spectra obtained in the pulse radiolysis of neat n-polyolen.
Figure 4 Transient absorption spectra of radical anions (a) and radical cations (b) of polymethyl-
phenylsilane at 15, 100, and 250 nsec after a pulse. Superimposed gures indicate the kinetics traces of
transient absorption.
on the reaction mechanisms including main-chain scission and cross-linking induced by the
irradiation of low-LET radiation such as
60
Co g-rays, high-energy electron beams, etc.
Throughout these studies, the mainandgeneral objective was todevelopanunderstanding of
the dierent chemical reactions that occur when a polymer is subjected to radiation and to
relate these to observed changes in physical properties. Pioneering studies of the simplest
polymeric material, polyethylene, were started by Dole [65] and Charlesby [66] in 19481952,
demonstrating the drastic improvement in the thermal stability and insolubility for solvents.
Since this pioneering study, radiation-induced reaction mechanisms in polyethylene have
been vigorously and extensively investigated in detail, which brought up many questions in
the fundamental aspects of radiation chemical processes in polymeric materials.
Dose Rate. The dose rate factor is closely related to the atmosphere, temperature,
shape of irradiated specimen, etc.; thus the eect of dose rate is hardly discussed separately
from the others. An accumulation of reactive intermediates such as radicals basically plays
an important role in the dose rate eects in the ratio of main-chain scission and cross-linking
reactions. The accumulation, namely, the density of reactive intermediates, is a slowprocess
competing with the consumption by reaction with the molecules in the atmosphere, radical
recombination, etc., as well as the consumption by other reactions such as double bond
formation. In many cases of irradiation with relatively high dose rate by high-energy EB,
these eects may often be neglected because the consumption by atmospheric molecules
occurs via diusion in a polymeric material. However, the eects become crucial for cross-
linking in reactive atmosphere such as hydrogel formation or grafting [67], radiation-
induced conductivity measurement [68], or sterilization [69] by ionizing radiation. These
eects also play an important role in the ultra-high-density energy deposition by charged
particles, and will be discussed later.
Figure 5 Transient absorption spectra of irradiated additive-free solid PMMA containing MMA
monomers observed by the authors improved nanosecond pulse radiolysis system over a wide range
of temperatures and with the monitoring wavelength region from 300 to 1600 nm.
Temperature. Temperature determines the chain motion of irradiated polymer
molecules and is easily predicted to be a crucial factor controlling the eciency of the
reactions induced by radiation. Cross-linking reactions in polyethylene showed a large
dependence of the yield on its crystallinity, suggesting the motion of the chain (ends) directly
controls the eciency of cross-linking and main-chain scission. The yield of cross-linking
tends to be higher with an increase in the irradiation temperature. One of the recent typical
examples was reported by Oshima et al. for the radiation-induced reactions in poly(tetra-
uoroethylene) (PTFE) [70]. PTFE was so sensitive to ionizing radiation that its mechanical
properties degrade with either a very low dose in air or even under vacuum irradiation, and
this had been considered a typical main-chain scission type polymeric system. Oshima et al.
reported that the cross-linking reactions of PTFE became predominant by the irradiation at
its molten state just above the melting temperature (608 K) under oxygen-free atmosphere,
and antichemical solvents, high frictional properties, and cross-linked PTFE shows remark-
able improvement in radiation resistance, mechanical properties, frictional properties,
visible light transparency, and so on, compared with non-cross-linked PTFE. There is no
other way to attain the cross-linked PTFEthan by the above technique. Similar temperature
eects were also observed for polycaprolactone, which showed a remarkable increase in the
yield of cross-linking at the temperature above its melting point (333 K), keeping the high
yield even at RT in the quenched specimen [71]. The inverse eects of temperature on the
radiation-induced cross-linking were observed in poly(di-n-hexylsilane) of which liquid
crystalline transition temperature was 313 K. The polymer indicated ecient formation of
cross-linking for EB and ion beam irradiation at RT; however, the predominant reaction
abruptly changed into main-chain scission at above that temperature for the same radiation
sources. This was mainly attributed to the reduction of very ecient main-chain scission
reaction by radical recombination within the tightly packed crystalline phase of the
polymers, providing an exceptional example of radiation-induced cross-linking reactions
[72].
Structures. Stereotacticity is also an important factor that determines the eciency
of main-chain scission and cross-linking. Polypropylene is one of the sensitive polymers in
which radiation-induced reaction depends on the stereoregularity of the polymer backbone.
Wei et al. reported that G values of H
2
and CH
4
became smaller with increasing isotacticity
of polypropylene, suggesting the higher yield of cross-linking reaction in polypropylene with
higher isotacticity [73]. Reduced yield of main-chain scission reaction was also reported in
syndiotactic polystyrene in comparison with that in stactic polystyrene by Takashika et al.
[74]. Remarkable dierences in the G values of H
2
were also recorded in atactic and
syndiotactic polystyrene. The tacticity itself was also aected by the irradiation. High-
temperature irradiation with g-rays caused the reduction of isotacticity of isotactic PMMA
[75]. The changes were mainly caused by temporal main-chain scission followed by
recombination. The trace of the tacticity change enabled the evaluation of the eciency
of temporal main-chain scission, G(TCS), giving G(TCS) = 18.6, which was much higher
than the G value of permanent main-chain scission. The high value of G(TCS) is also very
important to reveal the amount of the potential reactive intermediates, hence for the fate of
energy deposited by radiation in the polymeric system.
3.4. Reaction Mechanisms of Electron Beam and X-Ray Resists
Electron beam resist has been a key material for mask fabrication in the semiconductor
industry. EB and x-ray lithography have recently attracted much attention as not only a
next-generation lithography in the semiconductor industry but also a nanofabrication tool
in the eld of nanotechnology and science. Under these circumstances, the research and
development of resist materials for EB and x-ray lithography have become more important
than ever. Many types of EB and x-ray resists have been developed. Details of these resists
will be discussed in Sec. 19.4.1. In this section, the radiation-induced reaction mechanisms of
resists are described.
Conventional resists such as PMMA and chlorinated poly(methylstyrene) (CMS) uti-
lize main-chain scission or cross-linking reactions induced by radiation. As the reaction
mechanisms of conventional resists have been reviewed in many books [76], this section will
be focused on the reaction mechanisms of chemically amplied EBand x-ray resists expected
as a next-generation resist for mass production. For chemically amplied resists, the latent
images are at rst formed with the acids generated by an exposure. The acids catalyze the
reactions such as a deblocking reaction to form real pattern in the following lithographic
process, typically during postexposure bake (PEB). In this process, the chain reactions by
acid catalysis enhance resist sensitivity. Since the role of radiation is to generate acids in
polymer matrix, acid-generation processes will be discussed.
Onium salts have been widely used as an acid generator for photo-, EB, and x-ray
resist. In addition, aromatic polymers such as novolak and polyhydroxystyrene have been
often used as a base polymer for EB and x-ray resist. The reaction mechanisms in a typical
resist system have been investigated by pulse radiolysis [43,52,7788], SR exposure
[79,80,8385], and product analysis [88]. Figure 6 shows the acid-generation mechanisms
induced by ionizing radiation in triphenylsulfonium triate solution in acetonitrile. The
yields of products from electron beam and KrF excimer laser irradiation of 10 mM
triphenylsulfonium triate solution in acetonitrile are shown in Fig. 7 to clarify the
Figure 6 Acid-generation reaction mechanisms induced by ionizing radiation triphenylsulfonium
triate solution. Percentages in the scheme are contributions of each reaction to total acid generation
for the 10 mM triphenylsulfonium triate in acetonitrile.
dierence between photoresist and radiation resist. In the case of KrF excimer resist, the
acid-generation processes mostly start from the direct excitation of onium salts. The main
products from the decomposition of excited sulfonium salts are in-cage recombination
products. This means the main proton source is hydrogen in the phenyl moiety in sulfonium
salts. Contrary to the photoinduced reaction, the reaction path from the excitation of
sulfonium salts accounts little for the yields of acids by EB and x-ray exposure [88].
In EB and x-ray lithography, the energy of radiation is deposited on resist materials
mostly via an ionization process. Cation radicals of base resin and electrons are generated by
the ionization. The electrons generated by ionization lose their energy through the
interaction with surrounding molecules and eventually thermalized. The initial separation
distance on average is thought to be approximately several nanometers, depending on the
type of materials. Cation radicals of base resin produce proton adducts via ion molecular
reaction with the base resin. In the case of novolak, the protons originate in the hydroxyl
groups of novolak. Therefore, the yield of acids is thought to be inuenced by the protection
of hydroxyl groups, which are often partially protected in the polarity change type resists.
For chemically amplied EB and x-ray resists, not only the dissolution characteristics of the
resists, but also the eciency of acid generation should be considered when hydroxyl groups
are protected in the design of the chemically amplied resists.
Onium salts scavenge electrons generated by ionization and release counteranions of
acids. As for various kinds of acid generators including nonionic acid generators, the rate
constant of their reactions with solvated electrons in methanol was evaluated [85]. All of
these are greater than 1.0 10
10
M
1
sec
1
and are considered to be diusion-controlled
reactions. The acids are thought to be formed through the recombination reaction of the
proton adducts with decomposed anions of onium salts. The electron- scavenging eect of
onium salts delays the recombination of cationic intermediates with electrons and prolongs
the lifetime of cationic intermediates. Yields of proton adducts increase with this eect.
Figure 7 Yields of products from electron beam and KrF excimer laser irradiation of 10 mM
triphenylsulfonium triate solution in acetonitrile.
In the chemically amplied resists, both the cation radicals of base resin and the
electrons generated by the ionization play an important role in the formation process of
acids [77]. Therefore, the geminate recombination of the cation radical of base resin with the
thermalized electrons is predicted to cause the decrease of the sensitivity. In addition, the
migration of thermalized electrons is predicted to cause the severe degradation of space
resolution of resists. The high eciency of reaction of oniumsalts with thermalized electrons
blocks both the geminate recombination and the migration of thermalized electrons in the
resist matrix. This prevents the degradation of sensitivity and spatial resolution of the resist
caused by the behavior of the thermalized electrons. This mechanism works well in the
current chemically amplied resists with spatial resolution around 100 nm. As the
dimension of resist pattern becomes closer to the initial separation distance of thermalized
electrons, the thermalization process and the subsequent reaction become more important.
The initial separation between cation radicals and electrons should be considered in the
resist design for nanolithography, as well as the scattering of secondary electrons and the
diusion of acids.
4. INDUSTRIAL APPLICATION OF RADIATION TO POLYMERS
4.1. Electron Beam and X-Ray Resists
With the advent of microelectronics, the human society has progressed to a highly
sophisticated information-oriented state. Microelectronic circuits have been fabricated
with a high resolution printing technique called lithography. The advance of micro-
electronics has highly depended on the technological innovation of lithography. Light
sources have changed toward shorter wavelength from the g-line (436 nm) of a Hg lamp to
the i-line (365 nm) of a Hg lamp to a KrF excimer laser (248 nm). An ArF excimer laser
(193 nm) is ready to be deployed as an exposure tool for mass production. An F
2
excimer
laser (157 nm) is being researched as the next-generation light source following the ArF
excimer laser. However, the resolving power of light sources will fall short of the market
demand in the near future. Radiation sources such as electron beam and x-ray are
expected to take the place of the light sources. Furthermore, nanotechnology has recently
attracted enthusiastic attention in many elds such as materials science, bioscience, and
information technology. EB and x-ray lithography are also promising tools for the mass
production of nanostructures. Research and development of each element such as a resist,
optics, and a mask for EB and x-ray lithography have been pursued. Especially, the resist
is a key technology for mass production and has been investigated energetically.
Mass production poses strict requirements on resist materials, most important of
which are sensitivity, spatial resolution, contrast, and etch resistance. The sensitivity of the
next-generation resists is required to be less than 10 AC/cm
2
(EB), 100 mJ/cm
2
(x-ray), and 25
mJ/cm
2
(EUV) [89]. It should be noted that the resist sensitivity is traditionally expressed not
by absorbed dose but exposure charge or energy per unit area. As for the spatial resolution,
45 nm is needed for the production of dynamic random access memory (DRAM) in 2010
[89]. Although resist patterns below 10 nmare presently fabricated by some kinds of resists,
they do not have enough sensitivity required for the mass production [90,91].
Electron beam lithography has been widely used in mask fabrication for photolitho-
graphy. X-raylithographyhas beenalsousedfor the fabricationof micromachines suchas the
LIGA(Lithographie, Galvanoformung, Abformung) process [92]. Manytypes of resists have
been developed for these purposes. Some positive and negative resists for EBlithography are
listed in Tables 1 and 2, respectively.
From the necessity of higher sensitivity resists than conventional ones, a chemically
amplied resist was developed originally for photolithography by Ito of IBM [93]. The
concept of chemically amplied made a great impact on lithography. Chemically
amplied resists have been used on a full scale in the mass-production line of semi-
conductors since the KrF excimer laser was deployed as an exposure source. The use of
chemically amplied resists is also one of the most promising technologies in EB and x-ray
lithography. Many types of chemically amplied resists have been developed and many
kinds of acid generators, cross-linkers, dissolution inhibitors, and resins have been
reported as shown in Table 3. Although chemically amplied resists based on acid
catalytic chain reaction mechanisms show high performance such as high sensitivity and
high contrast, they have very narrow process latitudes compared with conventional resists.
The sensitivities of chemically amplied resists tend to be degraded by impurities as these
depend on prebake temperature, prebake time, PEB temperature, PEB time, delay time
from exposure to development, and shelf life, among others. These problems are common
among photo, EB, and x-ray resists. Early researches focused on these problems to make
the chemically amplied resists applicable to the process lines, while the development of
new chemically amplied resists have been pursued [94100]. The feature required for the
next generation is so small that line-edge roughness and pattern collapse during develop-
ment are also problems and have been investigated [101,102]. Line-edge roughness should
be less than 5.5 nm (3 sigma) in the production of DRAM in 2010 [89].
Although single-layer resists are preferred from the viewpoint of simplicity of the
process, two- or three-layer resists are also promising [103]. These resists have an advantage
Table 1 Typical Conventional Positive EB Resists
Poly(methyl methacrylate)
Poly(butenesulfone)
Poly(hexauorobutylmethacrylate)
Poly(triuoroethyl-a-chloroacrylate)
Poly(methacrylic acid-co-phenylmethacrylate)
Poly(2-methylpentene-1-sulfone)/novolac
Poly(dimethyltetrauoropropylmethacrylate)
Poly(glycidylmethacrylate-co-hexauoropropylmethacrylate)
Poly(a-chloroacrylate)
Poly(isobutylene-co-methylmethacrylate)
Poly(methyl-isopropenylketone)
Poly(acrylonitrile-co-methylmetacrylate)
Table 2 Typical Conventional Negative
EB Resists
Poly(glycidylmethacrylate)
Epoxy poly(butadiene)
Poly(ethylacrylate-co-glycidylmethacrylate)
Chlorinated poly(methylstyrene)
Poly(iodostyrene)
Chlorinated poly(methylnaphthylmethacrylate)
over the single-layer resists in that multilayer resists can allot dierent roles to each layer.
Typically, a top layer bears the role of patterning and lower layers have the responsibilities
for etch resistance and planation of the substrate surface. Surface imaging technique is also
one of the candidates of the next-generation processes [104]. Imaging by silylation of
commercially available resists was reported. These techniques are expected to be useful
especially for EUV and a low-energy (a few kilovolts) EB lithography such as low energy e-
beam proximity projection lithography (LEEPLE).
In recent progress, calixarene resists have been prominent [105]. Hexaacetate p-
methylcalix[6]arene was demonstrated to work as a high-resolution negative resist. This
resist also shows high etch resistance. Calixarene resist has an advantage in its molecular
size (about 1 nm). Liquid crystal resists and inorganic resists show high resolution [106].
These resists are suitable for the fabrication of nanostructures. However, the resist
sensitivities are lower than those of chemically amplied resists, even PMMA.
It has been reported that the incorporation of nanoparticles such as fullerene and
oligosilsesquioxane (POSS) to resist matrix improves the resist performance such as etch
resistance and mechanical properties [107]. These resists are called nanocomposite resists.
A single-component chemically amplied resist that incorporates not only POSS but also
an acid generator into its main chain has been reported [108].
Although many types of excellent resists have been developed based on novel ideas,
the requirements for the next-generation resists have not yet been achieved. The quest for
the ultimate resist materials will continue.
4.2. Other Applications of Radiation to Polymers
Preparation, characterization, and fabrication of nanostructured materials have elicited
great interest in viewof their possibility of innovation in science, industry, environment, and
in our daily lives in the twenty-rst century. The research eld called nanoscience or
nanotechnology has been expanded and widespread since the end of the last century, and
the trend is expected to be wider and accelerated in this and in the next decade. Current
interest in the nanostructured materials predominantly comes from their unique physico-
chemical properties on account of their nite small sizes giving peculiar eects such as
Table 3 Typical Chemically Amplied EB Resists
Resist Component Type
No name Poly(4-tert-butoxycarbonyloxystyrene) Positive
[IBM] Acid generator
SAL series Novolak resin Negative
[Shipley] Cross-linker
Acid generator
RAY-PN (AZPN100) Novolak resin Negative
[Hoechst AG] Melamine cross-linker
EXP Novolak resin Positive
[NTT] 2,2-bis(t-Butoxycarbonyloxyphenyl)-propane
bis( p-t-Butylphenyl)iodonium triuoromethanesulfonate
PTBSS Poly(4-tert-butoxycarbonyloxystyrene-co-sulfur dioxide) Positive
[AT & T]
quantum size eect and quantum entrapment. Recent progress on the nature of nano-
structured materials has revealed unique electronic, magnetic, optical, and mechanical
properties, and the application of these properties has already started in industry. As
introduced in the previous section, nanoscale materials, to say nothing of their importance
in the semiconductor industry, are also expected to play a crucial role in the integrated
electronic circuit in the near future, which is obvious in the well-known Moores law and its
leading road map of semiconductor manufacturing.
In view of the preparation and fabrication of nanostructured materials, there are
apparently two kinds of trends. One is the assembling of molecules or atoms by using their
nature such as self-organization, self-reproduction, selective reaction, and condensation,
which is called bottom-up technology, to prepare the nanostructured materials. The other
approach, called the top-down technique, producing very small structures by using the
reaction caused by charged particles and photons, has been the major trend of micro- and
nanofabrication to date, and will be a key technology even in the future, because it is
necessary to prepare the interface of nanostructured materials for their real application even
if the materials themselves are produced by the bottom-up technique.
It has been considered that the most important advantage of radiation-induced re-
actions in the fundamental research is their nonselectivity in the media or spatial homoge-
neity of deposited energy, hence the distribution of reactive intermediates. It has been the
basic feature of radiation chemistry, not only in polymeric systems but also in organic and
inorganic systems, which has given much benet to us as an accurate quantitativeness
typically represented by G values. However, this nonselective and homogeneous concept is
no longer valid for the reaction induced by high-LET radiation including ion beams, which
has been suggested by the theoretical aspects on track structure in the condensed media. The
ultrahigh density of excitation and ionization within a charged particle track produce
extremely nonhomogeneous distribution of reactive intermediates along a particle trajec-
tory. The density of the excitation, ionization, and intermediates cannot be realized by any
other physicochemical techniques, and has potentials to cause brand-new chemical
reactions in the matter. If the yield of a chemical reaction can be controlled by the density
of the intermediates, we can freely control the size of the nonhomogeneous eld of chemical
reaction, which is called a chemical core, because the density of deposited energy is
basically presented as the function of radial distance from a particle trajectory.
Several experimental studies on the particle track suggested that the size of the
chemical core is controllable by selecting the target media and/or chemical treatment after
irradiation within the range froma fewto a fewtens of nanometers, which shows the best t
to produce the nanosized materials. An incident charged particle promotes a top-down-style
nonhomogeneous eld of chemical reaction, and its high controllability is provided by the
bottom-up nature of the target material. This is the concept of the complex of top-down and
bottom-up styles, which is one of the practical examples of radiation chemistry contributing
to nanoscience and nanotechnology.
Basics. It has been suggested that spatial distribution of deposited energy by charged
ions has played a signicant role in chemical reactions occurring in the target materials.
Models of the energy distribution were proposed experimentally and theoretically such as
Track Core and Penumbra models by Magee and Chattarjee (for a review, see Ref.
109), Katz et al. [110], Waligorski et al. [111], Varma et al. [112,113], Wingate and Baum
[114], Wilson [115], and other groups. In spite of the theoretical modeling eort, there are
still unknown factors in the relationship between the ion track structure and the values of
track radii that were experimentally obtained by the analysis of irradiation products
[72,116118].
As one of the basic formulations accounting for the radial dose distribution in an ion
track, the following formulas were given [92]:
q
c
r
LET
2
pr
2
c

1
LET
2
2pr
2
c
ln
e
1=2
r
p
r
c
h i
1
rVr
c
q
p
r
LET
2
2pr
2
ln
e
1=2
r
p
r
c
h i
1
r
c
<rVr
p
5
where q
c
and q
p
are the deposited energy density at the core and the penumbra region,
respectively, r
c
and r
p
are the radii of the core and the penumbra, respectively, and e is the
base of natural logarithm.
Experimental approaches to measure the radial dose distribution are also in progress
[119], and it was found that the distribution follows r
2
law in the inner region of a critical
distance and obeys r
3
law outside of that region. LaVerne and Schuler reported the
considerable decrease in the radiation chemical yield for ferric production in the Fricke
dosimeter, suggesting a model of a deposited energy density in an ion track, which depends
on the LET and the atomic number of an irradiation particle [120,121].
Puglisi and Licciardello [122], Licciardello and Puglisi [123], and Calcagno et al. [124]
also reported the eects of ion beambombardment to polystyrene leading to the aggregation
of molecules and cross-linking reactions. The abnormal change in molecular weight
distribution was ascribed to the intratrack reaction; however, the estimated size of ion
tracks was also larger than that of the track core. In many cases, the eects of the intratrack
nonhomogeneous reaction have been presented as the LET eects on the chemical yield of
radiation-induced reaction in the polymeric system. The LET eects on the yield of cross-
linking reaction were reported in polystyrene [125], polyethylene [126], polysulfone
[126,127], and polysilane [72,116,128], showing remarkable increase in the yield with an
increase in the value of LET of incident particles. Especially, polysulfone and polysilane
showed a drastic conversion from scission type (for low LET) to cross-linking (for high
LET) with the threshold value of LET [72,126]. Decrease in the yield of main-chain scission
was also observed in PMMAwith an increase in the LET. This experimental evidence can be
explained in part by the model of the nonhomogeneous reaction in an ion track in which
high-density reactive intermediates cause an increase in the yield of radical recombination,
cross-linking reaction, excited-state relaxation, cross-recombination of charges, etc. Ion-
beam-induced chemical reaction in other media was reviewed in other books [129] or
proceedings, and the present section introduces the present status of application of charged
particles in relation with nanoscience and nanotechnology.
Charged Particles for Nanofabrication. The basic approaches to nanofabrication by
using the nonhomogeneous reaction for nanofabrication can be divided into the next two
concepts: (1) making pores in polymer lm along a particle track and lling with metals,
semiconductors, ceramics, polymers, etc. and (2) directly making a wire along an ion track
based on the target polymer materials. The schematic view of these ideas is displayed in
Fig. 8. The rst approach surpasses the second in the choice of the materials to make, and the
second can prepare more precise structures of sizes smaller than 10 nm. The rst approach
began from the preparation of membranes having several microsized pores produced by
etching of charged particle tracks in nuclear materials (for reviews, see Refs. 130 and 131).
The concept of etched ion track and its lling was rst presented by Vetter and Spohr in 1993
[132] and at almost the same time by Ferain and Legras [133]. Their investigations were done
in parallel and overlapped with each other.
The attempt to use the membrane as the template of metallic replicas was successful for
preparation of copper whiskers on the substrate [132]. Vetter and Spohr used polycarbonate
membranes with a thickness of 10150 Am, and the lms were irradiated by heavy-ion beam
(Xe and heavier). The irradiated lms were etched by alkaline solution, and the etched pore
sizes were controlled by the time of the treatment. The copper metal was deposited by
electrolysis in a galvanic cell, and after the deposition, the membrane was removed
mechanically or by a suitable solvent. Figure 9 shows the SEM image of copper
microwhiskers on the substrate prepared by the above technique. The size of the whiskers
was a few micrometers as for the diameter of the cross section in this image. Fundamental
studies on the mechanism of etching processes have shown remarkable progress in the
controllability of the size of the etched pores [134], and are going on still now with the
collaboration of other groups to produce a drug-releasing system [135], thermoresponsive
membrane [136], etc.
Similar approach has also been taken by Ferain and Legras [133,137,138] and De Pra et
al. [139] to produce nanostructured materials based on the template of the membrane with
etched pores. Polycarbonate lm was also of use as the base membrane of the template, and
micro- and nanopores were formed by precise control of the etching procedure. Their most
resent report showed the successful formation of ultrasmall pores and electrodeposited
materials of which sizes were as much as 20 nm [139]. Another attractive point of these
studies is the deposited materials in the etched pores. Electrochemical polymerization of
conjugated polymer materials was demonstrated in these studies, and the nanowires based
on polypyrrole or polyaniline were formed with a fairly cylindrical shape reecting the side
wall structure of the etched pores. Figure 10 indicates the shape of the polypyrrole
microwires with their dimension changes by the limitation of the thickness of the template.
Figure 8 Schematic view of the two dierent concepts to prepare nanostructured materials using
chemical reactions in a particle track (chemical core). Bar length: 10 Am.
The direct formation of nanostructured materials was rst reported by Seki et al. as the
nonhomogeneous cross-linking reactions of polysilane giving nanogels or nanowires
along a particle trajectory in the polymer [72,116,140]. The schematic procedure to obtain
isolated nanowires is presented in Fig. 8. An incident ion deposits its energy densely within
a limited area, and a cross-linked, cylinder-like structure is formed along the projectile. The
uncross-linked part of a lm is washed by solvent, leading to the isolated nanowires of
cross-linked polysilanes. Figure 11 shows a series of atomic force microscope (AFM)
images for nanowires formed on a Si substrate, together with the enlarged view of a wire
and the schematic of a cross section. The section of a wire indicates a complete cylindrical
shape. The number of observed nanowires in a unit area shows good agreement with that of
incident particles. In spite of a development procedure by solvents, the wires remain
adhered to the Si substrate and the nanowires remain isolated from each other. This
indicates that one end of the wire is tightly connected to the substrate by chemical bonds.
Another interesting feature of the wires is their length. The lm with 170-nm initial
thickness is used to obtain the images in Fig. 11. The mean length of the nanowires in Fig.
11 is 180 F9 nm, suggesting that the length of a wire is fairly controlled by simply changing
the thickness of a target lm. Figure 12 shows the AFM images of the nanowires produced
in polysilanes with a variety of molecular weights and by the dierent ion beams. The
structure of the nanowire apparently changes from a thick rodlike to a ne wormlike wire
with a decrease in the molecular weight, and reects the lm thickness as the length of
nanowires. The thickness of the nanowire obviously depends also on the LET of ion beams.
Figure 9 Overview of copper whisker array prepared by electrodeposition in the membrane with
micropores, and dissolution of the polymer matrix by a solvent.
The formation of nanowire by the nonhomogeneous reaction brought up the need for a
new model dealing with the cross-linking reaction and gelation caused by high-LET
radiation on the basis of the nonrandom, nonhomogeneous spatial distribution of cross-
links. A preliminary expression of form for gel and sol fractions is given by [72]
s 1 r dr f g
f
g 1 1 r dr f g
f
6
where s denotes the fraction of a soluble part of a lm, g is the fraction of insoluble parts
reecting the total volume of the wires, r is the radius of a chemical track determined by
the energy deposition rate of an incident ion, dr is the dierential radius of the track, which
depends on the shape and size of an individual polymer molecule, and f is the uence of the
incident ion beams. The trace of the total volume of nanowires (gels) give the value of r in
the polymeric system for the incident charged particle based on the Eq. (6). The obtained
values of r show good agreement with those measured from AFM images of nanowires for
polysilane and heavy ions with high LET [140].
Figure 10 FE-SEM images of polypyrrole/C1O4 nanotubes obtained by electropolymerization in
the pores of supported nanoporous template with thickness of 350 nm (a, b, c) and 1.3 Am (d).
Figure 11 AFMimages of the nanowires. (a) Top viewobserved after development of nonirradiated
lms. Images (b), (c), and (d) indicate the surface morphology of the developed lms of poly(methyl-
phenylsilane) after ion irradiation by 450-MeV
129
Xe
23+
at 2.2 10
9
, 7.1 10
9
, and 1.1 10
10
ions/
cm
2
, respectively. The tone changing fromdark to bright in this gure implies the height as much as 24
nm. The enlarged view of a nanowire is observed for the same specimen as in (c).
The nonhomogeneous reaction caused by high-LET charged particles is a unique
technique to produce nanosized cylindrical structures. It not only produces isolated
nanowires on substrate but also controls the size and length of wires. It is needless to say that
homogeneous processes by radiation have played a very important role in the radiation
chemistry; however, nonhomogeneous processes might take part in future technologies as a
powerful tool for the preparation of nanostructured materials, although the process is a
rather extraordinary case in the eld of conventional radiation chemistry.
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Figure 12 Changes in the sizes of the nanowires. Images (a), (b), and (c) are the top view of
nanowires formed by the irradiation of 450-MeV
129
Xe
23+
to a poly(methylphenylsilane) (PS) (Mn =
4.2 10
5
) lm at 700-nmthickness, a PS (Mn =1.5 10
5
) lm at 400-nmthickness, and a PS (Mn =
5.0 10
3
) lm at 180-nm thickness, respectively. (d) Observed for a PS (Mn = 4.2 10
5
) lm at 310-
nm thickness irradiated by 520-MeV
84
Kr
20+
.
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20
Charged Particle and Photon Interactions
in Metal Clusters and Photographic
Systems Studies
Jacqueline Belloni and Mehran Mostafavi
UMR CNRSUPS, Universite Paris-Sud, Orsay, France
1. INTRODUCTION
A century ago, the reduction of silver ions in photographic plates helped W. Roentgen [1],
then H. Becquerel [2], to discover x-rays and radiation of radioactive elements, respec-
tively. Various metal ions were subsequently used widely in aqueous solutions as radical
scavengers and redox indicators of the short-lived primary radiolytic species, allowing
their identication and the calibration of their yield of formation [35]. Some underwent
reduction by g
[6] or pulse radiolysis [7] to the zero-valence metal, to form colloids and
then precipitates [7,8].
Due to the accurate knowledge of the dose used, a control of the progressive extent of
the radiolytic reduction was achieved. However, quite often, puzzling data were reported
when the zero-valent metal was formed, such as an induction time for precipitation, a
sensitivity of the radiolytic yields to the initial presence of added particles, and an unusually
weak reproducibility [9,10]. Moreover, oxidation of silver atoms by molecular oxygen was
observed [7], although the process was thermodynamically improbable for a noble metal
such as silver.
It was also observed, in 1973, that the fast reduction of Cu
+
ions by solvated electrons
in liquid ammonia did not yield the metal and that, instead, molecular hydrogen was
evolved [11]. These results were explained by assigning to the quasi-atomic state of the
nascent metal, specic thermodynamical properties distinct from those of the bulk metal,
which is stable under the same conditions. This concept implied that, as soon as formed,
atoms and small clusters of a metal, even a noble metal, may exhibit much stronger
reducing properties than the bulk metal, and may be spontaneously corroded by the solvent
with simultaneous hydrogen evolution. It also implied that for a given metal the
thermodynamics depended on the particle nuclearity (number of atoms reduced per
particle), and it therefore provided a rationalized interpretation of other previous data
[7,9,10]. Furthermore, experiments on the photoionization of silver atoms in solution
demonstrated that their ionization potential was much lower than that of the bulk metal
[12]. Moreover, it was shown that the redox potential of isolated silver atoms in water must
be lower than that of the silver electrode, Ej(Ag
+
/Ag
met
)=0.79 V
NHE
, by the sublimation
energy of the metal equal to 2.6 V and Ej(Ag
+
/Ag
0
)=1.8 V
NHE
[13]. In the early 1980s,
an increasing number of experimental work emphasized, for metal or semiconductor
particles prepared by various ways in the gaseous and condensed phases, the nuclearity-
dependent properties of clusters of atoms or molecules [1417], theoretically predicted
earlier by Kubo [18]. For two decades, the importance of these fundamental aspects and the
consequences for various applications, from electronics to material science, catalysis,
photography, nonlinear optics, etc. have given rise to a new research domain focused on
the synthesis and properties of these mesoscopic phases.
The radiation-induced method, in the g- or pulse regime [19,20] and, to a certain
extent, the photo-induced method [21], provide a particularly powerful means to produce in
condensed media, metal, and semiconductor clusters frommonomers as precursors, to study
their properties and to understand the exotic phenomena which occur whenever a newphase
of oligomeric particles is formed in the bulk of a homogeneous mother phase [2226],
phenomena which are therefore rather frequent in physics and chemistry. Unlike a recent
reviewconcerning semiconductor clusters [19], the present chapter is specically focused on
metal clusters, induced by ionizing radiation or ultraviolet (UV)visible photons.
2. METAL CLUSTER NUCLEATION AND GROWTH
2.1. Principles of Metal Atom Formation
The specicity of the radiation-induced reduction of metal ion precursors into metal atoms,
which then coalesce into clusters, is attributable to strong reducing agents such as the
Figure 1 Arrhenius plot of the rate constant of the hydrated electron with silver cation Ag
+
.
(From Ref. 50.)
species solvated electrons e
solv
, and H
atoms arising from the radiolysis of liquids [27].

Thus, no reducing additive is necessary and no other product is formed. Because the
ionizing radiation penetrates throughout the solution, these species are produced in the
bulk everywhere in the surroundings of the ions. Due to their very negative redox potential
(Ej(H
2
O/e
aq
)=2.87 V
NHE
and Ej(H
+
/H
)=2.3 V
NHE
in water) [27], they easily reduce
metal ions up to the zero-valent state (Fig. 1). The reduction is achieved at room
temperature, so that the inclusion of clusters into thermo-sensitive systems is possible.
Generally, the reduction is achieved under deaerated conditions to avoid a com-
petitive scavenging of e
solv
and H
atoms by oxygen. These atoms are as homogeneously

distributed as the ions and the reducing species, and they are therefore produced at rst as
isolated entities. Similarly, multivalent ions are reduced by multistep reactions, including
disproportionation of intermediate valencies. Such reduction reactions have been observed
directly by pulse radiolysis for a variety of metal ions (Fig. 2), mostly in water [28], but
also in other solvents where the ionic precursors are soluble. Most of their rate constants
are known and the reactions are often diusion controlled.
In contrast, OH
radicals, which are formed concomitantly in water radiolysis [27],

are able to oxidize the ions or the atoms into a higher oxidation state and thus to
counterbalance the previous reductions. For that reason, the solution is generally added
with a scavenger of OH
radicals. Among various possible molecules, the preferred choice

is for solutes whose oxidation by OH
yields radicals, which are unable to oxidize the metal

Figure 2 Absorption spectra of silver atom Ag
0
(top) and charged dimer Ag
2
+
(bottom) complexed
by CN
[37], EDTA [37], and NH

3
[36,47] in solution. The spectra of uncomplexed Ag
0
and Ag
2
+
are
shown for comparison. (From Ref. 35.)
ions, but in contrast, exhibit strong reducing power. Such solutes are alcohols (such as 2-
propanol) or formate anions whose monoelectronic oxidized forms ((CH
3
)
2
C
OH, COO
)
are strong reducing free radicals (Ej((CH
3
)
2
COH/(CH
3
)
2
C
OH)=1.8 V
NHE
[29] at pH 7
and Ej(CO
2
/COO
)=1.9 V
NHE
) [30]. H
radicals (Ej(H
/H
2
)=+2.3 V
NHE
) oxidize
these molecules as well by H abstraction. Alcohol and formyl radicals can reduce, directly,
or via complexation with the ion, the metal ions into lower valencies or into atoms for
monovalent cations.
Some low-valency cations produced in early steps and at partial reduction are
immediately neutralized by the counter anion if the solubility product is quite low, and
they behave indeed as transient monomers able to coalesce into semiconductor clusters [19].
2.2. Cluster Nucleation
As the early species produced after reduction such as metal atoms, dimers and oligomers are
short-lived; time-resolved observations of the reactions of these transients are carried out by
the pulse radiolysis method, coupled with optical absorption or conductivity. Generally,
kinetics are studied in the absence of oxygen or a stabilizer, unless their specic interaction
has to be known. The earliest [7,8,20] and most complete data [3139] on the nucleation
mechanism were obtained on silver clusters. Indeed, silver may be considered as a model
system owing to the one-step reduction of the monovalent silver ions, hydrated or
complexed with various ligands, and to the intense absorption bands of the transient
oligomers (Fig. 2) and nal clusters (Fig. 3). The wavelength of the absorption band maxima
of the atom Ag
0
and of the charged dimer Ag
2
+
in aqueous solutions and the rate constants
of their formation are given in Table 1. Atoms and charged dimers of other metals, such as
Tl [40,41], In [42], Au [43,44], and Cu [42], are formed by homolog reactions (Table 1).
Figure 3 Left: Optical absorption spectrum and STM image of radiation-induced oligomers Ag
7
3+
at partial reduction and stabilized by PA [85,86]. Right: Absorption spectrum of radiation-induced
silver clusters Ag
n
in the presence of EDTA. (a) After partial reduction (10 krad), (b) after 4 days, (c)
after 8 days. Inset: TEM micrographs of (a), (b), (c), and electron diraction pattern of sample c.
(From Ref. 145.)
The band maxima of metal species are dierent in the gaseous and condensed phases.
The optical absorption bands of Ag
0
and Ag
2
+
are highly dependent on the environment
[45]. As shown in Table 1 and Fig. 2, the inuence of the interaction of ligands CN
, NH
3
,
or EDTA with the atom or the dimer is important [46]. The transient product of the
reduction in water of complexed silver ions is not the isolated atom but a complexed silver
atom, Ag
0
(CN)
2
2
[37], Ag
0
(NH
3
)
2
[47], or Ag
0
(EDTA) [37,48], respectively (Fig. 2), as well
as for Au
0
(CN)
2
2
[44] or CuCl
3
3
[42].
The optical absorption spectra depend on the solvent. They are red-shifted with the
decreasing polarity of the solvents as in EDA, liquid NH
3
, where they appear at a longer
wavelength than in water [49], and blue-shifted in methanol [38]. Moreover, the maximum
in NH
3
is red-shifted with the increase of temperature. In water, the Ag
0
band is almost
unchanged in the range 20200 jC, while that of Ag
2
+
is markedly shifted to the red [50].
Electron spin echo modulation analysis of Ag
0
in ice or methanol glasses has concluded to
a charge transfer character to solvent (CTTS) of the absorption band [51].
The multistep reduction mechanism of multivalent cations is known partially from
pulse radiolysis studies [19]. For example, the reduction of Au
III
Cl
4
into Au
II
Cl
3
and the
disproportionation of Au
II
into Au
I
and Au
III
have been directly observed and the rate
constants determined [52]. However, the last step of reduction of Au
I
complexed by Cl
into Au
0
is not observed by pulse radiolysis because the e
aq
scavenging by the precursors

Au
III
is more ecient. Moreover, the disproportionation of Au
I
or of other monovalent
cations is thermodynamically hindered by the quite negative value of Ej(M
I
/M
0
)(Ej(M
I
/
M
0
)<Ej(M
II
/M
I
)) (Section 20.4.4).
2.3. Cluster Growth
The binding energy between two metal atoms is stronger than the atomsolvent or atom
ligand bond energy. Therefore the atoms spontaneously dimerize when encountering or
associate with excess ions (Fig. 2). Then, by a cascade of coalescence process, these species
progressively coalesce into larger clusters M
n+x
y+
, where n represents the nuclearity, i.e.,
the number of reduced atoms they contain, x is the number of associated ions, and y
( y zx) is the charge number of adsorbed ions. When these ions are complexed by
negatively charged ligands, the cluster charge may be negative.
Table 1 Formation Rate Constants (mol l
1
sec
1
) and Optical Absorption Maxima of
Metal Atoms, Hydrated or Complexed, and of the Corresponding Charged Dimers in Water [19]
Metal Ions k
M
+
+e
aq
k (nm) of M
0
k
M
+
+M
0
k (nm) of M
2
+
Ag
+
3.6 10
10
360 [13,35] 8 10
9
290, 315 [13,35]
Tl
+
3 10
10
450, 260 [40,41] 1.4 10
9
700, 420, 245 [40,41]
In
+
500 [42] 1.5 10
9
310, 460 [42]
Ag(CN)
2
5 10
9
450, 500 [37] 2 10
10
350, 410, 490 [37]
Ag(EDTA)
3
1.7 10
9
400, 450 [37] 1.6 10
9
310, 340, 400, 475 [37]
Ag(NH
3
)
2
+
3.2 10
10
350 [8], 385 [47] 315, 340 [48]
Au(CN)
2
1.1 10
10
420 [43,44]
Ag
I
,PA 3.6 10
9
360 [39] 8.9 10
9
310, 450 [39]
Ag
I
, gelatin 1.1 10
10
360 [34] 1.1 10
10
290, 315, 308, 325 [34]
Cu(Cl)
3
2
2.7 10
10
380 [42] 4.9 10
7
360 [42]
The radius of M
n
increases as n
1/3
. The fast reactions of ion association with atoms or
clusters play an important role in the cluster growth mechanism. First, the homolog charge
of clusters slow down their coalescence. Second, the subsequent reduction in situ of the ions
xed on the clusters favors their growth rather than the generation of new isolated atoms.
The competition between reduction of free ions and of adsorbed ions is controlled by the
formation rate of the reducing radicals, that is, by the dose rate. Coalescence reactions obey
second-order kinetics. Therefore the cluster formation by reduction into isolated atoms
followed by coalescence is predominant at high irradiation dose rate, particularly in the
pulsed regime compared to continuous irradiation at much lower dose rate.
Moreover, almost in all the early steps, the redox potential of the clusters, which
decreases with the nuclearity, is quite negative. Therefore the growth process undergoes
another competition with a spontaneous corrosion by the solvent and the radiolytic protons,
corrosion which may even prevent the formation of clusters, as mostly in the case of
nonnoble metals. Monomeric atoms and oligomers of these elements are so fragile to reverse
oxidation by the mediumthat H
2
is evolved and the zerovalent metal is not formed [11]. For
that reason, it is preferable in these systems to scavenge the protons by adding a base to the
solution and to favor the coalescence by a reduction faster than the oxidation [53].
Figure 4 Growth kinetics of silver clusters observed through their absorbance at 400 nm in the
presence of (a) cyanide or (b) sulfate. (From Ref. 54.)
After the formation of Ag
0
and Ag
2
+
, followed by the reaction of Ag
2
+
with Ag
+
yielding Ag
3
2+
(k
max
=315 and 260 nm) [35], or its dimerization into Ag
4
2+
(k
max
=265 nm),
the multistep coalescence of oligomers result in clusters of increasing nuclearity Ag
n
. The
absorption spectrum is shifted to the surface plasmon band of Ag
n
at 380400 nm, the
coalescence rate depending on the ligand [54]. At the same initial concentration of atoms,
the plateau is reached at an almost 10
3
longer time for Ag
n
(CN
) [54] than Ag
n
(SO
4
2
) [31]
(Fig. 4). In methanol, the coalescence rate constants are also much lower [38]. Indeed, it is
known, according to the Mie theory [55] and its extension [56], that the interaction of light
with the electrons of small metal particles results in an absorption band whose shape and
intensity depend on the cluster size, the complex dielectric constants of the metal and the
environment (solvent, ligand, molecules adsorbed). During the coalescence, the total
amount of silver atoms formed by the pulse is constant, but they are aggregated into
clusters of increasing nuclearity n with a decreasing concentration. Thus the absorbance
increase observed at 400 nm (Fig. 4) is assigned to the increase with the nuclearity of the
extinction coecient per silver atom. It was shown from the kinetics analysis that the
plasmon band is totally developed with the constant value per atom e = 1.510
4
l mol
1
cm
1
beyond n=13. [57] Then, the coalescence into larger clusters is still continuing,
although the spectrum is unchanged.
3. REACTIVITY OF TRANSIENT METAL CLUSTERS
A number of rate constants for reactions of transients derived from the reduction of metal
ions and metal complexes were determined by pulse radiolysis [58]. Because of the short-
lived character of atoms and oligomers, the determination of their redox potential is
possible only by kinetic methods using pulse radiolysis. In the couple M
n
+
/M
n
, the reducing
properties of M
n
as electron donor as well as oxidizing properties of M
n
+
as electron
acceptor are deduced from the occurrence of an electron transfer reaction with a reference
reactant of known potential. These reactions obviously occur in competition with the
cascade of coalescence processes. The unknown potential Ej(M
n
+
/M
n
) is derived by
comparing the action of several reference systems of dierent potentials.
3.1. Redox Potentials of Metal Atoms and Dimers
The oxidation reactions of Ag
0
and Ag
2
+
[7,20], of Au
0
(CN)
2
2
[44], or of Tl
0
and Tl
2
+
[41,59], by even mild oxidizing molecules (O
2
, CCl
4
, CH
3
NO
2
, N
2
O, Fe
III
, for example) were
observed by pulse radiolysis. The high rate constants found indicate the strong electron
donating character of atomic silver, gold, or thallium. This conrms the evaluation of
Ej(Ag
+
/Ag
0
)=1.8 V
NHE
[13] and Ej(Tl
+
/Tl
0
)=1.9 V
NHE
[41], which were derived
from the dierence between the metal electrode potential, Ej(M
+
/M
met
), and the metal
sublimation energy (Table 2). More generally, because of the high value of the sublimation
energy, the potential of any metal Ej(M
+
/M
0
) is expected to be quite negative.
Table 2 Redox Potentials (V
NHF
) of the Hydrated and Complexed M
I
/M
0
Couple in Water
Couple
M
I
/M
o
Au
+
/
Au
0
Cu
+
/
Cu
0
Tl
+
/
Tl
0
Ag
+
/
Ag
0
Ag(CN)
2
/
Ag
0
(CN)
2
2
Ag(NH
3
)
2
+
/
Ag
0
(NH
3
)
2
Ag(EDTA)
3
/
Ag
0
(EDTA)
4
Ej 1.4 [44] 2.7 [13] 1.9 [41] 1.8 [13] 2.6 [36,61] 2.4 [47] 2.2 [37]
The redox potential values of all metal atoms, except alkaline and earth-alkaline
metals [60], are higher than that of Ej(H
2
O/e
aq
)=2.87 V
NHE
. However, some complexed
ions are not reducible by alcohol radicals under basic conditions and thus Ej(M
+
L/
M
0
L)<2.1 V
NHE
(Table 2). The results were conrmed by SCF calculations of Ag
+
L
and Ag
0
L structures associated with the solvation eect given by the cavity model for
L=CN
[61] or NH
3
[47], respectively.
3.2. Redox Potentials of Oligomeric Metal Clusters
For clusters of higher nuclearity too, the kinetic method for determining the redox potential
Ej(M
n
+
/M
n
) is based on electron transfer, for example, from mild reductants of known
potential which are used as reference systems, towards charged clusters M
n
+
. [31] Note that
the redox potential diers from the microelectrode potential Ej(M
+
, M
n
/M
n
) by the
adsorption energy of M
+
on M
n
(except for n=1). The principle [31] is to observe at which
step n of the cascade of coalescence reactions, a reaction of electron transfer occurring
between a donor S
and the cluster M

n
+
could compete with the coalescence. Indeed, n is
known fromthe coalescence rate constant value, measured in the absence of S, and fromthe
time elapsed from the atom appearance to the start of coalescence. The donor S
is
produced by the same pulse as the atoms M
0
, the radiolytic radicals being shared between
M
+
and S. One form at least in the couple S/S
should possess intense optical absorption

properties to permit a detailed kinetics study.
The transfer requires that Ej(M
n
+
/M
n
), which increases when n becomes higher than
the reference Ej(S/S
), thus xing a critical nuclearity n

c
. As far as n < n
c
, the coalescence
occurs as in the absence of S
, whose concentration remains constant during an induction

time. As soon as the nuclearity increases, such as n z n
c
, the electrons are transferred from
S
to M
n
+
, which is thus indirectly reduced, and the S
concentration decreases. The donor

S
behaves as an electron relay. After the adsorption of another cation, the potential of the
new reduced cluster Ej(M
n+1
+
/M
n+1
) is more positive and another electron is transferred
from S
repeatedly. The clusters grow now mostly by alternate reactions of electron

transfer and adsorption of surrounding metal ions. It has been shown that once formed, a
critical cluster, of silver for example, behaves indeed as a nucleus of an autocatalytic growth
[31]. The branching ratio between the direct reduction of metal ions by radiolytic species
and the indirect reduction of M
+
by the donor is xed by the initial M
+
and S concen-
tration ratio. The distribution of nal sizes is totally governed by this competition because,
at the increasing S/M
+
concentration ratio, less nuclei are formed and they develop to
larger sizes [31].
The value of the critical nuclearity n
c
allowing the transfer from the monitor depends
on the redox potential of this selected donor S
. The induction time and the donor decay

rate both depend on the initial concentrations of metal atoms and of the donor [31,62].
The critical nuclearity n
c
corresponding to the potential threshold imposed by the donor
and the transfer rate constant value, which is supposed to be independent of n, are derived
from the tting between the kinetics of the experimental donor decay rates under various
conditions and numerical simulations through adjusted parameters (Fig. 5) [54]. By
changing the reference potential in a series of redox monitors, the dependence of the
silver cluster potential on the nuclearity was obtained (Fig. 6 and Table 5) [26,63].
Clusters M
n
+
may also behave as electron donors when formed in the presence of
oxidizing reactants. For example, as far as n <n
c
, a cascade of electron transfers fromM
n
to
S leading to corrosion of M
n
is possible because Ej(M
n
+
/M
n
)<Ej(S/S
), and it should be
taken into account in the simulation. This corrosion process is generally negligible because
the step of M
+
release is not fast enough. However, it is observed when the coalescence is
also slow, for example in the case of ions included in cavities of a Naon membrane, where
the coalescence of Ag
n
is controlled by the very slow diusion between the cavities (10
4
l mol
1
sec
1
) [64,65]. It has been found that the smallest clusters could be oxidized by the
protons H
3
O
+
, which are highly concentrated at the cavity surface. In contrast, when
clusters reach by coalescence the critical nuclearity for which their potential is higher than
Ej(H
3
O
+
/H
2
)=0 V
NHE
, they escape corrosion and are observed by optical absorption. The
Figure 5 Comparison between simulated and experimental decay of MV
+.
in the presence of
growing clusters Ag
n
,
CN
including oxidation of subcritical oligomers by MV

2+
and development of
supercritical clusters by MV
+
.
. The best t yields n
c
=5. (From Ref. 54.)
Figure 6 Size-dependence of the redox potential of silver clusters in water (.) [63] and of the
corresponding ionization potential in the gas phase (D) [67,68]. The redox potentials refer to the
normal hydrogen electrode whose Fermi potential is at 4.5 eV.
corrosion is particularly important when the dose per pulse is low and the coalescence is
slower (the nal amount of Ag
n
is 20 times less for a four times lower dose per pulse). The
numerical simulation of the kinetic signal including the cascades of coalescence and
oxidation reactions yields the value n=8 for the upper limit of nuclearity of silver clusters
oxidized by H
3
O
+
in the NaonR cavities [65]. Therefore, Ej(Ag
8
+
/Ag
8
) >Ej(H
3
O
+
/
H
2
)=0 V
NHE
. Contrarily, such a corrosion by H
3
O
+
is not observed under conditions of
free diusion of the clusters as in Ag
+
solutions [49], when the coalescence is much faster.
When silver or gold atoms are generated from Ag
I
(CN)
2
or Au
I
(CN)
2
in the
presence of the methylviologen redox couple MV
2+
/MV
+.
, oxidation of the smallest
clusters is also observed, because coalescence in cyanide solutions is slow (Fig. 4) [54,66].
While supercritical silver clusters (n > 6 F 1) (Table 3) accept electrons from MV
+.
with a
progressive increase of their nuclearity, the subcritical clusters undergo a progressive
oxidation by MV
2+
(Fig. 5). Actually, the reduced ions MV
+.
so produced act as an
electron relay favoring the growth of large clusters at the expense of the small ones. If
cyano-silver clusters require a higher nuclearity than aquo clusters to react with MV
+.
(Table 3), it means that the ligand CN
lowers the redox potential at a given n, as in the

case of the bulk metal. In the case of gold clusters complexed by cyanide, the coalescence is
still slower and oxidation of Au
n,CN
by MV
2+
is alone observed [66].
Fig. 6 compares the nuclearity eect on the redox potentials [19,31,63] of hydrated
Ag
n
clusters Ej(Ag
n
+
/Ag
n
)
aq
together with the eect on ionization potentials IP
g
(Ag
n
) of
bare silver clusters in the gas phase [67,68]. The asymptotic value of the redox potential is
reached at the nuclearity around n = 500 (diameter c 2 nm), which thus represents, for
the system, the transition between the mesoscopic and the macroscopic phase of the bulk
metal. The density of values available so far is not sucient to prove the existence of odd
even oscillations as for IP
g
. However, it is obvious from this gure that the variation of Ej
and IP
g
do exhibit opposite trends vs. n, for the solution (Table 5) and the gas phase,
respectively. The dierence between ionization potentials of bare and solvated clusters
decreases with increasing n as n
1/3
which corresponds fairly well to the solvation free
energy of the cation M
n
+
deduced from the Born solvation model [45] (for the single atom,
the dierence of 5 eV represents the solvation energy of the silver cation) [31].
A variation of Ej(Cu
n
+
/Cu
n
), similar to that of silver, is expected for copper because
the atomic potential is Ej(Cu
+
/Cu
0
)=2.7 V
NHE
[13] (Table 2), that of Cu, is Ej(Cu
7
+
/
Cu
7
) = 0.4 V
NHE
[69] (Table 5), and the bulk electrode potential is at 0.52 V
NHE
.
Table 3 Nuclearity-Dependence of Ej(M
n
+
/M
n
) (in V
NHE
) [63]
Reference System
(Electron Donor)
Ej(S/S
)
(Ref. Couple)
Metal Cluster
(Electron Acceptor) n
c
(Reduced Atoms/Cluster)
Ni
+
1.9 Ag
n
1
(CH
3
)
2
C
.
OH (pH 5) 1.8 Ag
n
1
SPV
.
0.41 Ag
n
4
Cu
+
0.16 Ag
n
11
Q
.
(pH=4.8)
a
0.22 Ag
n
85 F5
Q
.
(pH=3.9) 0.33 Ag
n
500 F30
MV
+
.
0.41 Ag
n.CN
56
MV
+.
0.41 Ag
n.PA
4
MV
+
.
0.41 Cu
n.Cl
6 F1
a
Q
.
is the semiquinone of naphtazarin.
Some calculations [70] were made to derive the microelectrode potential Ej(M
+
,
M
n1
/M
n
) for silver and copper from the data in the gas phase [nuclearity-dependent M
M
n
bond energy and IP
g
(M
n
)]. The potential Ej(M
+
,M
n1
/M
n
) presents oddeven
oscillations with n (more stable for n even) as for IP
g
, but again, the general trends are
opposite, and an increase is found in solution because to the solvation energy.
3.3. Nucleation, Growth, and Reactivity of Transient Bimetallic Clusters
The spectra of silver and gold nanoclusters are intense and distinct (Table 4). They are
thus particularly suitable to detect the evolution of a cluster composition during the
construction of a bimetallic cluster in mixed solution. The system studied by pulse
radiolysis was the radiolytic reduction of a mixed solution of two monovalent ions, the
cyano-silver and the cyano-gold ions Ag(CN)
2
and Au(CN)
2
(Fig. 7) [66]. Actually, the

time-resolved observation demonstrated a two-step process. First, the atoms Ag
0
and Au
0
are readily formed after the pulse and coalesce into an alloyed oligomer. However, due to
Table 4 Radiation-Induced Metal Clusters in Water
Metal
k
max
(nm) Ref. Metal
k
max
(nm) Ref. Metal
k
max
(nm) Ref.
Co UV [104,114] Pd 205 [84,110,112] Ir UV [88,105]
Ni* UV [53,104,115,116] Ag* 380 [8,31,35,57] Pt* 215 [52,92,93,106]
Cu* 570 [42,84,93,112,113] Cd* 260 [84,117,118] Au* 520 [43,44,52,107109]
Zn UV [104] In* 270 [42] Hg* 500 [42,104]
Mo UV [104] Sn 200 [104,119] Tl* 300 [4042,59,120]
Ru UV [104] Sb UV [104] Pb* 220 [42,104,121,122]
Rh UV [104] Os UV [104] Bi 253 [42,104,123]
* indicates that the earliest steps of the cluster formation have been studied by pulse radiolysis.
Figure 7 Correlated signals at 400 and 520 nm with a single pulse in equimolar mixed solution of
gold and silver cyanide, Ag(CN)
2
and Au(CN)
2
, in the presence of 2-propanol. (From Ref. 66.)

a slow electron transfer (within seconds) from Au
0
atoms of the alloy to the unreduced
ions Ag
I
, a supplementary formation of Ag
0
correlates with the complete dissolution of
Au
0
as in an intermetallic displacement.
Another way to favor the statistical reduction leading to alloyed particles of silver
and gold is to allow the clusters grow more rapidly, before any observable intermetal
transfer, and consequently to let their redox potential increase in order to lower the risk of
the displacement. This can be achieved through a fast chemical reduction by a donor S
at
an alloyed nucleus surface as for monometallic clusters (Section 20.4.4). The reaction
competing with the intermetal exchange is now the chemical reduction, which can be
very fast provided nuclei are present. In a pulse radiolysis study, the transient reduced
viologen formed by an electron pulse has been observed to react with the small alloyed
(AuAg)
n,CN
clusters and the developed alloyed clusters are stable toward segregation [66].
Their nal size is quite large because the ions reduced by the donor are concentrated on a
small number of nuclei. Moreover, it was found [66] that the redox potential of such
critically alloyed AgAu clusters is almost the same (0.4 V
NHE
at n
c
= 6) as that of the
more noble metal (silver in cyanide environment) [54].
4. SYNTHESIS OF STABLE MONOMETALLIC NANOCLUSTERS
Stability means that clusters do not undergo coalescence nor corrosion by the medium, at
least in the absence of oxygen. The quite negative value of Ej(M
I
/M
0
) and the dependence
of the cluster redox potential on the nuclearity have crucial consequences in the formation
of early nuclei, their possible corrosion or their growth. As an example, the faster the
coalescence, the lower is the probability of corrosion of the small clusters by the medium.
The property of stability oers the means to apply to these clusters a larger amount of
suitable characterization techniques than to transient oligomers.
Various applications (Sections 20.5.3 and 20.7.3) require that the synthesis of stable
clusters be as small as possible, and the coalescence should be prevented somewhat by a
stabilizer or a support. Moreover, stable metal clusters can be used as precursors to
synthesize, by functionalizing their surface, highly elaborated materials, acquiring specic
properties [21], For example, fullerene- [71,72] or pyrene-functionalized gold clusters [73]
are used as self-assembled photoactive antenna units which could serve as building blocks
in the design of light-harvesting systems.
4.1. Cluster Size Stabilization
Metal atoms formed by irradiation or any other method tend to coalesce into oligomers,
which themselves progressively grow into larger clusters and eventually into precipitates,
as found in early radiolytic experiments. However, for studying stable clusters or for
applications, the coalescence must be limited as in other chemical methods of cluster
synthesis [74], either by adding a polymeric molecule acting as a cluster stabilizer or by
generating the atoms in a conned structure where diusion is prevented. Some ligands
such as CN
under deaerated conditions, or ethylenediaminetetraacetic acid (EDTA) [37]

under complete radiolytic reduction conditions, are able by themselves to stabilize small-
sized particles (Fig. 3).
Functional groups of a polymer with high anity for the metal ensure the anchoring
of the molecule at the cluster surface, while the polymeric chain protects the cluster from
coalescing with the next one and thus inhibits, at an early stage, further coalescence
through electrostatic repulsion or steric hindrance. When metal clusters are to be prepared
by irradiation, the stabilizing polymers must be selected for their inability to directly
reduce the ions before irradiation. Various stabilizers have been studied [19]: poly(vinyl
alcohol) (PVA) [75], sodium dodecyl sulfate (SDS) [75,76], sodium poly(vinylsulfate)
(PVS) [77], poly(acrylamide) (PAM) [78,79] or poly(N-methylacrylamide) (PNPAM) [78],
carbo-wax [80], poly(ethyleneimine) (PEI) [81,82], polyphosphate (PP) [83], and gelatin
[84]. Some functional groups such as alcohol are OH
scavengers and these may contribute

to the reduction under irradiation. The nal size of metal clusters stabilized by these
polymers lies in the nanometer range but it increases with the ratio metal atoms/polymer.
Sodium polyacrylate (PA) is a much stronger stabilizer which allows the formation of
long-lived metal oligomers (Fig. 3) [85,86].
The coalescence of atoms into clusters may also be restricted by generating the atoms
inside conned volumes of microorganized systems [87] or in porous materials [88]. The
ionic precursors are included prior to irradiation. The penetration in depth of ionizing
radiation permits the ion reduction in situ, even for opaque materials. The surface of solid
supports, adsorbing metal ions, is a strong limit to the diusion of the nascent atoms
formed by irradiation at room temperature, so that quite small clusters can survive.
4.2. Long-Lived Metal Oligomers
Metal oligomers are stabilized at quite small nuclearity when formed at low dose in the
presence of polyacrylate PA [85]. From pulse radiolysis of Ag
+
PA solutions, it appears
that the very slow (10
5
1 mol
1
sec
1
) dimerization of Ag
4
2+
silver oligomers [39,89] (275
and 350 nm) results into a blue-silver clusters (n = 4) absorbing at 292 and 800 nm [90],
and stable in air for years (Fig. 3). The 800-nm absorption band is assigned to a cluster
ligand PA interaction [86,91]. Clear images by STM show at clusters of 0.7 nm with
atoms spaced by 0.25 nm (Fig. 3) [85]. Each cluster contains seven atoms (possibly with an
eighth atom in the central position). Because only four atoms were reduced, they
correspond to the stoichiometry Ag
7
3+
(or Ag
8
4+
).
Similarly, when PtCl
6
4
ions are irradiated in the presence of PA, which prevents
coalescence, most of the Pt atoms are found via STM imaging in the form of very small
platinum oligomers of 37 atoms only [92]. In the presence of PP, PtCl
6
4
irradiated so-
lutions present a UV band with a maximum at 215 nm [93]. About 20% of the initial signal
is lost by oxidation when the sample is exposed to air, the rest being stable. This result
again conrms that the redox potential of the smallest clusters is markedly shifted to the
negative values.
When CuSO
4
solutions are g-irradiated with PA at pH 10, new absorption bands at
292, 350, and 455 nm are observed, provided the reduction of copper ions is partial [94]. At
an increasing dose, the intensity of the peaks assigned to small, stabilized copper oligomers
decreases correlatively with the plasmon band increase which develops at 570 nm. The UV
species are very sensitive to oxygen. Under acidic conditions, large clusters are observed
but not the UV oligomers. A pulse radiolysis study of monovalent Cu
+
ions, complexed in
the presence of a high concentration of Cl
without polymeric stabilizer, has shown that

short-lived states of reduced copper corresponding to the early steps of growth also absorb
in the range 355410 nm [95].
Among the nonnoble metals that can be synthesized by radiation-induced reduction
in solution, nickel raises some diculties because the atom formation and aggregation
processes undergo the competition of oxidation reactions of highly reactive transients,
such as monovalent Ni
+
ion, Ni atom, and the very rst nickel oligomers. Nevertheless, in
the presence of PA, a new absorption band develops at 540 nm with increasing doses [96].
The formation of the same absorption band was observed by pulse radiolysis. It increases
simultaneously with the formation of the very rst Ni atoms and it is assigned to a cluster
ligand interaction. Because of the high reactivity of nickel oligomers, the band disappears
within 24 hr, even when solutions are preserved from oxygen, through a spontaneous
reaction with the solvent.
When the irradiation of metal ion solutions is performed in the presence of the lig-
ands CO or PPh
3
, metal reduction, ligandation, and aggregation reactions compete,
leading to reduced metal complexes and then to stable molecular clusters, such as Chini
clusters [Pt
3
(CO)
6
]
m
2
with m = 310 (i.e., 930 Pt atoms) [97], or other metal clusters [98].
The synthesis is selective and m is controlled by adjusting the dose (m decreases at high
doses). The mechanism of the reduction has been determined recently by pulse radiolysis
[99]. Molecular clusters [Pt
3
(CO)
6
]
5
2
have been observed by STM [100].
Colloidal supports, such as small colloidal SiO
2
particles, restrict the interparticle
diusion of silver atoms when formed by radiolysis of the ions at their surface. The silver
oligomers absorbing at 290 and 330 nmare observed by pulse radiolysis. They are stable with
respect to coalescence but they are oxidized by MV
2+
, O
2
, Cu
2+
, and Ru(NH
3
)
6
3+
[101].
4.3. Nanometric Metal Clusters
Most of mono- or multivalent metals, except alkaline and earth-alkaline metals, have been
prepared by g-radiolysis in the form of nanometric clusters, stabilized with respect to
further coalescence by polymers or simply by ligands. The nal size depends on the type of
polymer or ligand, on the ratio metal/polymer but also on the dose rate (Fig. 8) [19].
Indeed, sudden generation of a high concentration of isolated atoms at a high dose rate
yields, by coalescence, more numerous and smaller nuclei clusters (Fig. 8a) [102]. Instead,
the in situ reduction of adsorbed ions at the surface of clusters, which is predominant at
decreasing dose rate and which is not prevented by the polymer, contributes to the de-
velopment of less numerous growth centers and results therefore in larger clusters (Fig.
8b). In both cases, however, the nuclei generation being strictly reproducible, the dis-
tribution of long-term sizes presents an exceptional homodispersity. Table 4 presents the
maximum wavelengths of the surface plasmon absorption band of clusters as prepared by
radiolysis in water. They are in agreement with the Mie model [55,56]. Most of the clusters
absorbed in the UV and the nanocolloids are brown. The intense colors of some
ultradivided metals, red for gold (k
max
= 520 nm), yellow for silver (k
max
= 380 nm),
and pink for copper (k
max
= 570 nm) have been well known for a long time [56,74].
In solution, the particles are most often spherical. Nevertheless, some of these
clusters, which are generated in solution and then deposited on a grid for HRTEM and
electron diraction observations, exhibit clearly pentagonal shapes with an fcc structure,
which suggests the formation of twin fcc crystallites growing from the faces of an
icosahedral nucleus. Phase imaging in tapping-mode AFM is a powerful tool for the
characterization of clusters stabilized by polymer matrices as shown recently in observing
silver and gold samples [103], and helps to discriminate between amorphous polymer and
metal clusters.
Noble metal clusters have been most often studied (Table 4) [104], such as Ag
n
[8,31,35,57], Ir
n
[88,105], Pt
n
[52,92,93,106], Au
n
[43,44,52,107109], Pd
n
[84,110112], Ru
n
[104], Rh
n
[104], and Os
n
[104]. However, silver and gold clusters, when produced in the
presence of the ligand CN
[44,54,66], or in methanol [38], even at nanometric size, are

spontaneously corroded as soon as in contact with oxygen.
Nonnoble metal clusters are considerably more fragile to corrosion by the solvent
[11] compared to noble metal clusters. Therefore the production of stable small particles
results from a compromise between the smallest size and the longest stability [104].
Long-lived clusters, Cu
n
[42,84,93,112,113], Co
n
[104,114], Ni
n
[53,104,115,116], Cd
n
[84,117,118], Sn
n
[104,119], Tl
n
[4042,59,120], Pb
n
[42,104,121,122], Bi
n
[42,104,123], Hg
n
[42,104], In
n
[42], Mo
n
[104], and Sb
n
[104] (Table 4), may be formed in deaerated basic
medium, but Zn
n
[104] clusters are oxidized into zinc hydroxide within a few weeks even in
the absence of O
2
. Clusters Cd
n
are better stabilized by gelatin [84]. Ni
n
or Co
n
clusters
display ferromagnetic properties and at high concentration, and the sols behave as
ferrouids [124]. Whereas all of these nonprecious metal clusters are easily oxidized in
solution by O
2
, they may be stabilized in air after drying under inert atmosphere and
observed by microscopy [53].
Adsorption of ions or molecules on metal clusters markedly aects their optical
properties. It was shown that the intensity and the shape of the surface plasmon
absorption band of silver nanometric particles, which is close to 380 nm, change upon
adsorption of various substances [125]. The important damping of the band generally
observed is assigned to the change of the electron density of the thin surface layer of the
Figure 8 Nucleation and growth of clusters generated by radiolytic radicals at various dose rates,
with or without electron donor D. The stabilizing eect of the polymer prevents exclusively coa-
lescence beyond a certain limit of nuclearity, but does not prevent successive ion and electron
transfers at low dose rate from the radicals. The donor allows the cluster to become much larger at
any dose rate. (From Ref. 19.)
particle where electrons are, for instance, injected by adsorbed electrophilic anions [24].
This is followed by a red shift of the damped absorption band corresponding to loose
agglomeration of the clusters [126]. Silver particles covered by I
become particularly
sensitive to oxidation in air, because the Fermi level is shifted to a more negative potential
by the electron donation [24]. Likewise, binding of electronegative groups to the gold
surface leads to damping of the surface plasmon band of gold nanoparticles [127]. It was
shown that (SCN)
2
j
radicals generated by pulse radiolysis bind strongly to the gold

nanoparticles, oxidizing the gold clusters to form [Au(SCN)2]
[128].
Although the mechanism of the photo-induced generation of mono- and bimetallic
metal clusters, except for the photographic application (Section 20.6), has been studied
with considerably less detail than for the radiolytic route, some stable clusters, mostly of
noble metals (Ag, Au, Pt, Pd, Rh), have also been prepared by UV excitation of metal ion
solutions [129141]. Generally, halides and pseudo-halides counter anions are known to
release, when excited, solvated electrons, which reduce the metal ions up to the zerovalent
state. Oxalate excitation yields the strong reducing carbonyl radical COO
.
[30]. Photo-
sensitizers are likewise often added [142]. Metal clusters are photo-induced as well at the
surface of photo-excited semiconductors in contact with metal ions [143,144].
4.4. Developed Clusters
Actually, the kinetics study of the redox potential of transient clusters (Section 20.3.2) has
shown that beyond the critical nuclearity, they receive electrons without delay from an
electron donor already present. The critical nuclearity depends on the donor potential and
then the autocatalytic growth does not stop until the metal ions or the electron donor are not
exhausted (Fig. 8c). An extreme case of the size development occurs, despite the presence of
the polymer, when the nucleation induced by radiolytic reduction is followed by a chemical
reduction. The donor D does not create new nuclei but allows the supercritical clusters to
develop. This process may be used to select the cluster nal size by the choice of the
radiolytic/chemical reduction ratio. But it also occurs spontaneously any time when even a
mild reducing agent is present during the radiolytic synthesis. The specicity of this method
is to combine the ion reduction successively:
(i) By radiolytic reduction. The atoms independently formed in the bulk coalesce
into oligomers.
(ii) By chemical reduction beyond a certain oligomer nuclearity. This chemical
agent is unable thermodynamically to reduce the ions directly into atoms
(Section 20.3.1), but it achieves the reduction of the rest of the ions after they
have been adsorbed on the radiation-induced clusters acting as nuclei of
catalytic reduction and growth. Note that the polymer restricts the coalescence
of the nuclei or of the nal particles but does not prevent at all the development
by diusion and adsorption of excess ions and electron transfer from the donor
as shown for some of the following systems.
The nal silver cluster diameter increases, at given initial Ag
+
and PVA concen-
trations, for example from 15 to 50 nm (n 50 times larger), when the part of reduction is
increasingly achieved by the donor SPV
, rather than by radiolytic radicals [31]. A red

shift correlates with the growth in size in the nal optical surface plasmon band.
Nonirradiated solutions of EDTA silver complex are stable because EDTA does not
reduce the ions directly. However, after the appearance of the 400-nm spectrum of silver
clusters formed in a partially radiation-reduced solution (spherical particles of 1015 nm
diameter), the band intensity increases for days as a posteect and the silver ions are
totally reduced (Fig. 3) [37,145]. The postirradiation reduction is assigned to the lone pair
N atom electrons of the EDTA ligand, provided the silver ions are xed on clusters formed
by irradiation acting as nuclei. Once the development is over, the Mie band at 400 nm is
less intense and a new band appears around 1000 nm as the particle shape changed from
spherical to triangular pellets (large particles of 100150 nm). It is clear that this unusual
orientated growth favors the 111 surface.
Nickel oligomers prepared in the presence of PA (k
max
=540 nm) (Section 20.4.2)
may also act as catalysts for the reduction of Ni
2+
by hypophosphite ions. This requires,
as shown by pulse radiolysis, a critical nuclearity, while free Ni
2+
cannot be reduced
directly by H
2
PO
2
. Very low radiation dose conditions, just initiating the formation of a

few supercritical nuclei, will lead to large particles of nickel [96].
When trivalent chloro gold ions Au
III
Cl
4
are g-irradiated at increasing doses, the

reduction occurs by successive steps. However, Au
I
ions are not reduced as far as Au
III
ions are more concentrated than Au
I
, nor do they disproportionate because the redox
potential involving the single atom Ej(Au
I
/Au
0
) is quite negative (Table 2). Thus, Au
I
Cl
2
ions accumulate and the cluster appearance is delayed by an induction time [108]. With
higher doses, Au
I
ions become more abundant than Au
III
and are also reduced into atoms
and clusters. In the presence of alcohols or of preformed clusters, Au
I
ions do not
accumulate because the potential order of (Au
I
/Au
0
) and (Au
II
/Au
I
) couples is now
inverted as a result of complexation or adsorption, respectively. Au
I
ions are thus allowed
to disproportionate, giving rise to atoms and growing clusters. In addition, a very slow
chemical reduction by the alcohol is found, which occurs exclusively at the surface of the
clusters formed by irradiation so that all gold ions may be reduced, whatever the initial
dose [108]. As seen by AFM observations, the cluster size remains constant and their
concentration increases with dose during the g-irradiation, while during the postirradia-
tion reduction by alcohol the size increases at constant density of particles. The lower the
dose, the larger the nal size of the homodisperse cubic crystallites, which may range from
10 to 500 nm, depending on the respective parts of radiolytic and chemical types of
reduction.
Gold ions Au
I
(CN)
2
are not reducible in solution by alcohol radicals, owing to their

much lower redox potential in the complexed form [44], than in the hydrated form (Section
20.4.1 and Table 2). This was recently conrmed [109] by the observation of a very long
induction time before the appearance of the plasmon band of gold clusters generated by a
low amount of solvated electrons only. However, the complexed ions are reduced when
adsorbed at the particle surface and the gold clusters are developed to an extent depending
on added gold ion amount [146].
A stabilization of low valencies of metals and an induction time before cluster
formation have been observed as well in the case of iridium [105], platinum [53], palladium
[147], copper [94], or nickel [115].
The time-resolved studies of the cluster formation achieved by pulse radiolysis
techniques allow one to better understand the main kinetic factors which aect the nal
cluster size found, not only in the radiolytic method but also in other reduction (chemical
or photochemical) techniques. Generally, reducing chemical agents are thermodynami-
cally unable to reduce directly metal ions into atoms (Section 20.4) unless they are com-
plexed or adsorbed on walls or dust particles. Therefore, we explain the higher sizes and
the broad dispersity obtained in this case by in situ reduction on fewer sites. A classic
example is given by the reduction of silver ions by reducing additives. In the bulk of the
solution, the redox potential of the latter is not negative enough to reduce the ions into
free atoms. In contrast, due to the much more positive redox potential of the ions
adsorbed on walls of the reaction vessel, their reduction is allowed and the result is a silver
mirror.
4.5. Supported and Confined Nanoclusters
The radiolytic synthesis consists of: (1) either preparing rst nanometric metal clusters
in solution, which are then put in contact with the support (possibly by ltration), or (2)
irradiating in situ the ionic precursors after their adsorption onto the supporting material.
Positively charged metal ions easily diuse into the cavities of a NaonR polymeric
membrane by ion exchange of the counter cations of the constitutive sulfonic groups (Sec-
tion 20.4.2). The size of channels and cavities is controlled by the proportion of alcohol
in aqueous solution, which also governs the nal size of silver or nickel clusters after
irradiation [64]. During irradiation of a solution of metal ions (silver, palladium or nickel)
containing PVA without OH scavenger, the ion reduction occurs simultaneously with the
cross-linking of the polymer [25]. Finally, after drying, the clusters formed are trapped in a
polymeric lm. In the case of nickel, the thin lm is ferromagnetic. Irradiation of reverse
micelles containing gold ions in the aqueous phase generates small gold clusters [87]. Silver
oligomers (n<10) in AOT micelles absorb in the UV [148].
Iridium clusters supported on Al
2
O
3
or TiO
2
oxides were prepared by irradiation of
ions adsorbed on the oxides [149,150]. Radiation-induced grafting of Ir, Pt, or Ru clusters
was achieved on SnO
2
[151,152]. Optically clear aluminasilica xerogels with glassy aspect
containing silver clusters of 2.54.5 nm were also obtained [153,154]. Irradiation by MeV
ion beams of copper oxide containing glasses followed by a moderate thermal annealing at
673 K, allows the control of atom coalescence and to produce nanometric copper clusters
which are protected from further reaction by the glass matrix [155]. Homogeneously
dispersed Pt nanoparticles were obtained from radiolytic reduction of molecular carbonyl
clusters on carbon bers or powders [156,157]. It was shown by EXAFS that the prismatic
structure of radiation-induced Chini molecular clusters [Pt
3
(CO)
6
]
46
2
, when supported on
carbon under inert atmosphere, was transformed into a planar layer with conservation of
trimeric units, and partially into small fcc Pt clusters on contact with the air. On a-Al
2
O
3
,
larger particles are formed [158].
Irradiation by ionizing radiation, capable of penetrating into a zeolite material
exchanged by metal ions, allows the generation of metal atoms and clusters in situ in the
cavities [159161]. The observation of irradiated faujasite (NaY zeolite) by optical ab-
sorption spectroscopy at increasing doses and, at low silver content, demonstrates the
formation of two bands, at 265 and 305 nm, which have been assigned to the charged
trimer Ag
3
2+
. Then, the ESR observation, after a dehydration step, indicates the reduction
of this species into Ag
3
0
[162]. The photoreduction of H
2
PtCl
6
solution included in
mesoporous channels of molecular sieves induces nanowires of platinum [163]. Chini
molecular clusters of platinum carbonyl can also be synthezised in situ in these channels
(ship-in-bottle synthesis); then, they are photoreduced by UVvis light to nanowires of
2.5 nm diameter and 50300 nm length (Fig. 9) [137]. The temperature dependence of the
unique magnetic properties of these Pt nanowires has been studied.
Pulse radiolysis studies of the reactivity of 25-nm AgI particles with e
aq
in the
presence of alcohol have shown that, rst, the semiconductor spectrum at 360 nm is
bleached, then silver atoms and clusters at 450600 nm are formed [164,165]. The electron
Figure 9 Left: Schematic representation of chemical or UV-induced synthesis of Pt nanowires and
nanoparticles in zeolites FSM-16. Right: Comparison of temperature dependence of magnetization
for Pt nanowires and nanoparticles in FSM-16. (From Ref. 137.)
Figure 10 Size-dependence of the melting point and diusion coecient of silica-encapsulated
gold particles. The dotted curve is calculated by the equation of Buat and Borel. The bulk melting
temperature of Au is indicated by the double arrow as T
m
(l). The solid curve (right-hand side axis)
is a calculated Au self-diusion coecient. (From Ref. 146.)
transfer between the couple MV
2+
/MV
+.
and Ag
n
clusters formed on an AgCl crystallite
was studied by pulse radiolysis [166]. The coalescence of Ag atoms at the AgCl surface is
slow so that, as in the presence of CN
, an electron transfer from subcritical clusters to

MV
2+
precedes the electron transfer from MV
+.
to supercritical Ag
n
+
.
Recently, gold clusters of increasing size from 1.5 to 20 nm, after being chemically
prepared, radiolytically or by radiolytic enlargement, were coated with a silica shell [146].
Because the gold/silica concentration ratio is constant, the silica thickness increases upon
increasing the core size and is 5 nm at the maximum. For all particles, the melting point is
noticeably lower than that of the bulk. It decreases markedly with the cluster size, implying
an increase of the self-diusion of gold atoms, from 210
32
in the bulk to 10
24
cm
2
sec
1
for 2-nm clusters (Fig. 10).
5. SYNTHESIS OF BIMETALLIC CLUSTERS
Composite clusters, alloyed or bilayered, are of great interest because they enlarge the
number of the possible types of clusters and also of their applications. It is therefore
important to be able to select the conditions of the synthesis of composite metal clusters
containing M
0
and MV
0
in variable proportions, with either an alloyed or a core/shell
structure. The latter can be obtained by a two-step process [19,82,167171]. The method of
generating rst gold clusters radiolytically, which are then coated with a silver shell by
irradiating them in the second step in the presence of silver ions, was recently applied to
produce core/shell Au/Ag nanoparticles of 2.520 nm diameter [172]. The smaller the
initial gold core diameter (V4.6 nm), the more important is the spontaneous interdiusion
after a week at room temperature of both metals at the coreshell interface, leading to
alloying, which is detected by XAFS. The self-diusion of atoms increases upon decreas-
ing the cluster size [146], but the diusion coecient alone is too low to account for the
observations. However, the migration of atoms is catalyzed by vacancy defects present at
the interface [172].
Actually, when a mixed solution of two ionic precursors M
+
and MV
+
is irradiated or
chemically reduced, both situations of alloyed or bilayered cluster formation may be
encountered without clear prediction [102,173]. Moreover, an unambiguous character-
ization of the intimate structure of nanometric mixed clusters is quite dicult and requires
appropriate methods, applied at dierent steps (or dierent doses) of the mixed cluster
construction.
5.1. CoreShell and Alloyed Clusters Formation
In many cases, although M
+
and MV
+
are both readily reduced by radiolytic radicals, a
further electron transfer from the more electronegative atoms (for example, MV) to the
more noble ions M
+
(Ej(MV
+
/MV
0
)<Ej(M
+
/M
0
)) systematically favors the reduction
into M
0
. If the ionic precursors are plurivalent, an electron transfer is also possible
between the low valencies of both metals, so increasing the probability of segregation
[174]. The intermetal electron transfer has been observe directly by pulse techniques for
some systems [66,175,176], and the transient cluster (MMV)
+
sometimes identied such as
(AgTl)
+
or (AgCo)
2+
[176]. The less noble metal ions act as an electron relay toward the
precious metal ions, so long as all M
+
are not reduced. Thus, monometallic clusters M
n
are formed rst and MV
+
ions are reduced afterward in situ when adsorbed at the surface
of M
n
as in the cases of Ag/Cd [177], Ag/Cu [178], and Ag/Tl [120]. The nal result is a
coreshell cluster M
m
/M
n
V , where the more noble metal M is coated by the second MV.
In some other cases, the intermetal electron transfer does not occur even during
hour-long irradiations. The initial simultaneous reduction reactions of M
+
and MV
+
are
followed by mixed coalescence and association of atoms and clusters with ions, homolog
or not. Besides the dimerization of atoms of the same metal into M
2
and M
2
V , coalescence
of both types of atoms occurs twice more frequently. Subsequently, mixed coalescence and
reduction reactions progressively build bimetallic alloyed clusters according to the
statistics of encounters, therefore to the relative initial ion abundance [53].
5.2. Dose Rate Effects
The possible formation of an alloyed or a coreshell cluster depends on the kinetic com-
petition between, on one hand, the irreversible release of the metal ions displaced by the
excess ions of the more noble metal after electron transfer and, on the other hand, the
radiation-induced reduction of both metal ions, which depends on the dose rate (Table 5).
The pulse radiolysis study of a mixed system [66] (Fig. 7) suggested that a very fast and
total reduction by the means of a powerful and sudden irradiation delivered for instance
by an electron beam (EB) should prevent the intermetal electron transfer and produce
alloyed clusters. Indeed, such a decisive eect of the dose rate has been demonstrated [102].
However, the competition imposed by the metal displacement is more or less serious,
because, depending on the couple of metals, the process may not occur [53], or, on the
contrary, may last only hours, minutes, or even seconds [102].
The alloyed or layered character of a small bimetallic cluster structure is generally
quite dicult to conclude experimentally [102,179]. Even if the surface plasmon transitions
of both pure metals are specic (with one possibly in the UV), the unknown spectra of
alloyed or bilayered clusters are both expected in the same intermediate region. The
Table 5 Multimetallic Clusters
Synthesis and Irradiation Conditions
Mixed Salts
Dose Rate (kGy hr
1
)
Irradiation Source Particle Structure (Ref.)
Ag(CN)
2
, Au(CN)
2
g, 35 Ag/Au, Bilayer [102]

Ag(CN)
2
, Au(CN)
2
EB, 7.9 10
3
AgAu, Alloy [102]
Ag
+
, AuCl
4
g, 3.8 Au/Ag, Bilayer [102]

Ag
+
, AuCl
4
g, 35; EB, 7.9 10

3
AgAu, Alloy [102]
Ag
+
, Cd
2
+
g, 0.87 Ag/Cd, Bilayer [177]
Ag
+
, Pd
2
+
g, 35 AgPd, Alloy [180]
Ag
+
, PtCl
6
2
g, 30 AgPt, Alloy [183]
Ag
+
, Tl
+
g, 0.6 Ag/Tl, Bilayer [119]
AuCl
4
, PtCl
6
2
EB, 7.9 10
3
; g, 0.540 Au/Pt, Bilayer [184]
Au(CN)
2
, PtCl
6
2
EB, 7.9 10
3
; g, 0.540 Pt/Au, Bilayer [184]
Cu
2+
, Cd
2+
g, 0.42, 0.48 CuCd, Alloy [83,182]
Cu
2+
, Pd
2+
g, 30 CuPd, Alloy [53]
AuCl
4
, Pd
2+
g 35 Au/Pd, AuPd, Bilayer [181]
AuCl
4
, Pd
2+
EB, 7.9 10
3
Au/Pd, AuPd, Alloy [181]
Ag
+
,Rh
2+
g, 35 Rh, Ag, Segregation [185]
Ag
+
, Rh
2+
EB, 7.9 10
3
Rh, Ag, Segregation [185]
structure of the composite cluster should be derived indeed from the evolution observation
of the absorption spectrum at increasing dose during the cluster building [102,180,181].
Because the spectrumis attributable to surface phenomena, it changes with dose if one metal
is preferentially reduced rst. The surface composition of a bilayered cluster is shifted at
increasing dose from the spectrum of the more noble metal to that of a cluster coated by the
second. In contrast, the spectrum shape of alloyed clusters is unchanged at increasing dose
while the intensity increases. X-ray analysis of clusters at partial reduction (increasing dose)
clearly indicates at each step whether atoms of only one or of both types of metals are present
in the particles [102]. In the case of an alloyed cluster, electron and X-diraction methods
may reveal superlattices that correspond to a perfectly ordered atom arrangement
[4,99,140]. Provided that the lattice constants of the metals are somewhat dierent, the
distances between atomic plans in HRTEM images may indicate the possible alloyed
character of clusters.
For example, when the mixed solution of Ag(CN)
2
and Au(CN)
2
is irradiated by
g-radiolysis at increasing dose, the spectrum of pure silver clusters is observed rst at
400 nm, because Ag is more noble than Au due to the CN
ligand. Then, the spectrumis red-

shifted to 500 nmwhen gold is reduced at the surface of silver clusters in a bilayered structure
[102], as when the cluster is formed in a two-step operation [168] (Table 5). However, when
the same system is irradiated at a high dose rate with an electron beam, allowing the
sudden (out of redox thermodynamics equilibrium) and complete reduction of all the ions
prior to the metal displacement, the band maximumof the alloyed clusters is at 420 nm[102].
Similarly, at moderate dose rate for the couple Au
III
Cl
4
, Ag
+
, gold initially appears at
520 nm. Therefore, Ag
+
ions essentially act as an electron scavenger, and as an electron
relay toward more noble gold ions as far as gold ions are not totally reduced. Then silver-
coated gold clusters are formed and the maximumis shifted to 400 nm, which is that of silver
(Fig. 11) [102]. But at higher g- or EB dose rate (irradiation time of a few seconds), the
electron transfer is too slowto compete with coalescence and the spectrumof alloyed clusters
Figure 11 Evolution with increasing irradiation dose of the absorption spectra of a mixed solution
AuCl
4
/Ag
+
(50/50). Left: with PVA at a dose rate of 3.8 kGy hr
1
. Right: 35 kGy hr
1
. Dotted
line: spectrum with PA. Inset: Evolution with increasing dose of the absorbance at k=480 nm.
(From Ref. 102.)
surrounded by Cl
develops at 480 nm without any shift from the lowest doses (Fig. 11).
Once this quenching radiolytic reduction has consumed all the ions, the intermetal displace-
ment becomes in fact excluded at roomtemperature. In both cases, low- and high-dose rates,
a transverse analysis of a single cluster in a scanning transmission electron microscope
equipped with a eld emission gun and x-ray detector conrmed the cluster composition in
depth, bilayered and alloyed, respectively [179].
The same evolution of the absorption spectrum with the dose has been found in a
high dose rate for various values of the Ag and Au ion fraction in the initial solution.
Clusters Ag
1x
Au
x
are alloyed with the same composition. The maximum wavelength k
max
and the extinction coecient e
max
of the alloy depend on x. The experimental spectra are
in good agreement with the surface plasmon spectra calculated from the Mie model at x
values for which optical data are available (Fig. 12) [102]. Similar calculations were carried
out for the alloy Ag
x
Pd
1x
obtained at a moderate dose rate [180].
Figure 12 Top: Maximum wavelength of the plasmon band of alloyed goldsilver clusters as a
function of the mole fraction x of gold in alloyed goldsilver clusters, produced at the dose rate 7.9
MGy hr
1
and the dose 20 kGy. . Experiments, 5 calculated values by Mie model. Bottom:
Extinction coecient at the maximum of the plasmon band as a function of the mole fraction x of
gold in alloyed gold-silver clusters. . Experiments, 5 calculated values from Kreibig equation [74]
with r = 5 nm; D with r = 3 nm. (From Ref. 102.)
The same contrast between bilayered and alloyed clusters of AuPd has been observed
at low- and high-dose rate, respectively [180], by using spectrophotometry, EDAX, and XPS
analysis at partial and complete reduction.
Other examples of bimetallic clusters are presented in Table 5. Depending on the rate
of the intermetal electron transfer competing with the dose rate-dependent coalescence
(Fig. 13 and Table 5):
1. Alloying may occur spontaneously, even at low reduction rate (g-irradiation
with low dose rate) [53], as for alloyed Cu3Pd [53], CuPd [53], NiPt [53], CuCd
[84,182], AgCd [177], Ag
x
Pd
1x
[180], and AgPt clusters [183].
2. Alloying may require higher g-dose rates as for Ag
x
Au
1x
[102].
3. Alloying is only obtained through a short and intense irradiation provided by an
electron accelerator as for Ag
x
Au
1x
[102], and AuPd [180].
4. Alloying is even not obtained. In extreme cases, the electron transfer is achieved
within times shorter than the irradiation time required for complete reduction
Figure 13 Scheme of the inuence of the dose rate on the competition between the inter-metal
electron transfer and the coalescence processes during the radiolytic reduction of mixed metal ion
solutions. Sudden irradiation at high dose rates favor alloying, whereas low dose rates favor core
shell segregation of the metals because of metal displacement in the clusters.
(a few seconds with EB) and, in spite of the very fast reduction, metals are
segregated into coreshell structures (Au/Pt, [184]) or into distinct clusters (Ag
n
and Rh
n
) [185]. For multivalent ion precursors, intermetal electron transfer
reactions may also occur between the transient lower valency ions.
5.3. Catalytic Properties of Metal Clusters
One of the important applications of mono- and multimetallic clusters is to be used as
catalysts [186]. Their catalytic properties depend on the nature of metal atoms accessible to
the reactants at the surface. The possible control through the radiolytic synthesis of the
alloying of various metals, all present at the surface, is therefore particularly important for
the catalysis of multistep reactions. The role of the size is twofold. It governs the kinetics
by the number of active sites, which increase with the specic area. However, the most
crucial role is played by the cluster potential, which depends on the nuclearity and controls
the thermodynamics, possibly with a threshold. For example, in the catalysis of electron
transfer (Fig. 14), the cluster is able to eciently relay electrons from a donor to an
acceptor, provided the potential value is intermediate between those of the reactants [49].
Below or above these two thresholds, the transfer to or from the cluster, respectively, is
thermodynamically inhibited and the cluster is unable to act as a relay. The optimum
range is adjustable by the size [63].
Figure 14 Mechanism of catalytic electron transfer involving metal clusters as relay. The thermo-
dynamic conditions to be fullled are that the cluster redox potential be higher than the donor D and
lower than the acceptor A potential, which implies that the cluster itself is a size range that oers the
ecient redox potential. (From Ref. 63.)
Clusters, as possible catalytic reactors, are perfectly dispersed in solutions. They are
thus suitable systems for observing, under quasi-homogeneous conditions by time-
resolved techniques, the kinetics of catalyzed electron transfer, which would be inacces-
sible on a solid catalyst. It was demonstrated that the reaction of radiation-induced free
radicals CO
2
.
and (CH
3
)
2
C
OH catalyzed by metal clusters started by the storage of

electrons on clusters as charge pools and that electrons were then transferred pairwise to
water-producing molecular hydrogen [22,75].
The mechanism of the electron transfer from electron donor such as MV
+
to H
+
producing molecular hydrogen and catalyzed by Au [187] or Pt clusters [188], and that of the
disproportionation reaction of the superoxide radical anion O
2
by Pt clusters in solution or
supported on colloidal TiO
2
particles [189], have been studied by pulse radiolysis.
In some examples, the reaction catalyzed by radiation-induced clusters was studied
during long periods under the conditions of a pilot system to compare their properties with
catalysts prepared by chemical reduction. They easily fulll the conditions of controlled,
nanometric and homodisperse size, of alloying for multimetallic clusters and of strong
grafting on various supports. They were found ecient catalysts, for example, in the case of
alumina-supported iridium clusters for hydrazine decomposition in thrusters developed for
spacecraft orbit and attitude control systems [88]. Radiation-induced mono- and multi-
metallic clusters imbedded in NaonR [64] or grafted on metal [190], on SnO
2
transparent
counterelectrodes [152,152], or on carbon electrodes [25,100] were found to be quite active
in electrochemical, photovoltaic, and fuel cells (methanol or hydrogen oxidation), respec-
tively. Multimetallic clusters deposited on gelatine silver bromide emulsions are excellent
catalysts for silver reduction in the oset process [191] The catalytic performances of photo-
induced Pt nanowires in zeolites were tested by using the watergas shift reaction [137].
6. PHOTOGRAPHY
Silver photography [192195], and later, radiography [1,2], are the oldest applications of
the unique properties of oligomers, long before the mechanisms were understood. The time-
resolved techniques were particularly helpful to improve our understanding of the intimate
reaction process. Since its invention, innumerable improvements to photography have been
introduced to capture an image as close as possible to our vision of the light intensities and
the colors of a scene, and to enhance the photosensitivity of the photographic layer.
However, the basic principle of silver photography lies on the photosensitivity to visible
light of minute silver halide crystals, which are xed in a gelatine layer as a mosaic. Each
crystal will behave as a picture element (pixel). During exposure, the light generates clusters
of a few silver atoms on the crystals. Their ensemble constitutes the latent image which is of
an extremely weak intensity and therefore invisible. Then the development consists of
converting chemically into metal particles the crystals containing a cluster with a super-
critical number of photo-induced silver atoms and of catalytically transforming the latent
image into a visible picture. In the last step of xing, undeveloped crystals which are still
photosensitive should be eliminated and are dissolved by complexation. The result is the
negative image, which is then used as a mask to produce the positive image.
6.1. Photographic Development
It is well known from photographic experience that critical nuclearity, which is required
for the development, depends on the redox potential of the developer (it is an electron
donor in excess in the development bath). Subsequently, the autocatalytic growth does not
stop until all the metal ions of the exposed crystals containing supercritical clusters are not
exhausted and the crystals transformed into silver metal grains. For over a century,
numerous theoretical models have been proposed, without success [196,195], to explain
how the supercritical clusters created by the light act as nuclei to catalyze development.
Trautweiler [197] had the intuition in his speculative model that the ionization potential of
supercritical sizes should lie above that of the developer. However, the only data then
available did not conrm this view.
Actually, the kinetic study of the cluster redox potential by pulse radiolysis [31]
(Section 20.3.2) somewhat mimics the process of the black-and-white photographic
development, except that clusters are free in the solution (not xed on AgBr crystals),
and that they are produced by ionizing radiation (as in radiography and not by visible
photons; but the last choice had been incompatible with the time-resolved optical detection
in the visible. Beyond the critical nuclearity, they receive electrons without delay from the
developer already present (actually, the photographic development is achieved in a delayed
step).
However, the similarity of the features presented by the processes in both cases,
reduction catalyzed by supercritical clusters in solution and photographic development on
AgBr crystals, allows us to extend to photographic development the same mechanism
demonstrated by pulse radiolysis [31,198]. Consequently, the mechanism results from the
increase of the cluster redox potential with the nuclearity when the developer solution is in
contact with silver bromide crystals. It explains the existence of a critical size in the
photographic development, and the threshold of the discrimination between underexposed
and exposed crystals for complete reduction is imposed by the rst monoelectronic redox
potential of the developer. It also explains the sensitizing eect [66] of gold ions more
noble than Ag
+
, and the fragility to oxidation of the smallest clusters of the latent image
[5]. With standard developers and sulde-gold sensitization, the amplication of the
cluster size by the development is from the critical number [194] n
c
=3 to n=10
89
, that
is the total number of silver ions in the AgBr crystal (about 1 Am).
Apart from the development in photography, most of nucleation and growth
mechanisms based on a chemical reduction (Section 20.4.4) behave as development
processes, and are likewise controlled by the nuclearity dependence of the cluster redox
potential and by the potential of the electron donor.
6.2. Enhancement of Photographic Sensitivity
According to the GurneyMott model [199], the primary light eect on a AgBr crystal is to
produce as many electronhole pairs (e
h
+
) as photons absorbed. The hole corresponds
to the electron vacancy created by the electron photoejection. The electron reduces a silver
cation into an atom, generally close to a sensitizer adsorbed at specic surface sites of
AgBr (sulde or/and gold centers). Then a cation adjacent to the atom and constituting a
charged dimer is reduced by another electron, and so on, the result being a cluster of a few
atoms. But an important part of electrons are lost by direct recombination with the parent
holes, before these diuse to the surface where they are irreversibly scavenged by gelatine
and additives (Fig. 15, top, left). Holes are also able to oxidize the newly formed silver
atoms, so counterbalancing somewhat the reduction by electrons (indirect recombination).
If R is the fraction of initial pairs lost by both types of recombination, and U
theor
=
1 pair/photon the theoretical quantum yield, the eective quantum yield U
e
is U
e
=
U
theor
(1R). In sulde/gold sensitized crystals, the yield is about U
e
= 0.100.30
(the fraction R is thus 0.900.70). Thus, apart from the absorption properties and the area
of the crystal, the photosensitivity of a lm depends directly on the quantum yield of the
cluster formation.
A recent approach to enhance the sensitivity was to specically scavenge the holes,
faster than their possible recombination with the electrons or the atoms, with the help of a
dopant [200]. In addition to a small size and an ionic character to allow its inclusion in the
AgBr crystal, the dopant should obey other strict criteria concerning the redox potential.
The dopant should be a bielectronic donor with a very weak rst redox potential, in order to
let the dopant scavenge the holes, without spontaneously reducing free Ag
+
and producing
fogging in the dark, and with a very negative second redox potential, to avoid a possible
hole-like behavior of the dopant oxidized form, so blocking any reversible oxidation
(Fig. 15, top, center). In addition, a second silver ion can be reduced (Fig. 15, top, right).
From radiation chemical knowledge, the anion formate HCO
2
fullls all the conditions, at

Figure 15 Top: Photographic latent image formation in undoped (left) and formate-doped and
gold-sulde sensitized AgBr crystals with the hole-scavenging step (center). Secondary reduction step
by formyl radical (right). Bottom: Sensitometry curves for gold-sulde sensitized emulsions, undoped
or formate-doped, and developed after 5 or 20 min (t
exp
=10
2
sec, development with aminophenol
and ascorbic acid). The same absorbance is observed for a number of photons absorbed 5 or 10 times
less, respectively, than in the undoped emulsion. (From Ref. 200.)
least in solution (Ej(CO
2
.
/HCO
2
)=1.07 V
NHE
and Ej(CO
2
/CO
2
.
)=1.9 V
NHE
in water)
[30].
Sensitometric tests at variable light intensity I under conditions of photography,
achieved on emulsions doped at the relative concentration of 10
6
mol HCO
2
per mol
Ag
+
, conrmed the photo-induced bielectronic transfer (Fig. 15, bottom) [200]. The
emulsion is completely stable in the dark. The number of photons required to induce
development of the same grain population fraction is 5 times less (after immediate
development) or 10 times less (development delayed by 20 min after exposure) in doped
than in undoped emulsions where U
e
=0.20. The quantum yield is thus close to the
theoretical limit U
e
=1 atom/photon in immediately developed doped emulsion (R=0),
and U
e
=2 atom/photon if the development is delayed for 20 min, and the slow additional
reduction of a silver ion by CO
2
.
can occur, thus doubling the gain. An important sen-
sitivity enhancement is similarly observed for dye-sensitized crystals [200]. These doping
studies [200,201] not only provide a better understanding of the mechanism of the latent
image formation, but also oer a promising route for improving the performance of all
kinds of silver emulsions, for black-and-white and color photography, radiography, holog-
raphy, etc.
7. CLUSTER FORMATION AND CLUSTER EXCITATION BY POWERFUL
LASERS
Metal clusters exhibit intense optical absorption due to the surface plasmon band, some
in the visible spectrum (Table 4). The response to light excitation is linear as far as the
source is of weak intensity. However, other phenomena appear when pulses of extremely
high intensity are used. A burst activity has been seen in recent years in the area of inter-
action of light from powerful laser pulses with metal in order to produce nanoparticles by
laser ablation, or with nanoparticles in order to let them absorb suddenly a high amount of
energy and to observe the transient and the irreversible eects on the clusters. Eventually, a
change in the morphological shape induced by the laser or a fragmentation of nanoclusters
may occur (Fig. 16).
7.1. Nanoparticles Formation by Laser Ablation
The method of laser ablation from a metal has been used to prepare nanoparticles dis-
persed in a solution [202207]. Recently, colloidal gold nanoparticles in water having an
average diameter of 5.5 nm were prepared by laser ablation at 1064 nm (800 mJ/cm
2
) from
a gold metal plate [208]. The nal nanoparticle size depends on the laser uence and the
stabilizer concentration (Fig. 17).
7.2. Nanoparticles Melting and Fragmentation
Gold clusters can be tailored by subjecting them to melting or to fragmentation and
bimetallic nanoparticles can be alloyed after melting under irradiation by a pulsed laser at
532 nm in the vicinity of the wavelength of the surface plasmon band [209212]. In fact, the
electrons of the plasmon band are highly excited. The hot electrons transfer the energy to
the lattice in less than a fewpicoseconds. The transfer can occur before or after the electrons
have reached thermal equilibrium (Fig. 16). Eventually, the energy of the phonons is trans-
ferred to the surrounding solvent.
If the laser pulse is very short and its energy high enough, the temperature of the
lattice can reach several thousands degrees. Depending on the energy of the pulse, melting,
fragmentation, and even vaporization of the particles is thus possible. It was shown that
silver and gold clusters undergo signicant morphological change under laser irradiation.
Gold nanorods can be transformed into spherical particles by exciting the metal clusters
with femtosecond laser pulses (Fig. 18) [211]. The amount of energy needed to transform a
gold nanorod into a sphere is more than 60 fJ. The time corresponding to the melting is
around 35 psec, which is shorter than the period required for the energy transfer from the
lattice to the solvent (100 psec). Therefore, sucient energy is accumulated by the lattice
arising from photon absorption and the temperature increases enough to melt and change
the morphology of the gold nanorods. Therefore, if the laser energy increases above the
threshold of melting, the fragmentation channel becomes open. Transmission electron
microscopy (TEM) measurements of nanorods irradiated by a high-energy nanosecond
laser pulse clearly showed that the nanorods are fragmented into small spheres.
Figure 16 Scheme of the successive events following the interaction of a high uence laser pulse
with metal clusters. First, the energy is conned in a hot cluster, then the eects depend on the
uence and on the cluster surface to volume ratio. Low uence: the energy is transferred to the
solvent, which expands into bubbles scattering the light; meantime, the cluster is reversibly cooled
without change of the shape. Medium uence: the cluster temperature is high enough to obtain
cluster melting and changing to spherical shape. High uence: the energy conned within the cluster
creates a fast step of expansionvaporization of the metal particle which acts as a light scattering
center. After the energy has been transferred to the solvent, the solvent bubbles become secondary
light scattering centers and the metal vapor condenses into fragmented clusters. Eventually, the
solvent bubbles cool down by energy dissipation to the bulk.
7.3. Optical Limitation Induced by Nanoparticles
The nonlinear optical properties of nanoclusters were also studied as potential light
limitation systems [213]. The nonlinear optical response of gold particles (of 5-, 10-, or 30-
nm diameter, the latter being enlarged by development) prepared by g-radiolysis in water
solution and stabilized by PVA is size-dependent. The threshold and the amplitude of
limitation depend on the particle size (Fig. 19). At a given total atom concentration, the
light transmission at 532 nm of nanosecond laser pulses at very high uence is weakly
limited by 5-nm clusters, but strongly limited by the 30-nm clusters. The optical limiting
eect induced by gold clusters, measured as a function of the excitation wavelength,
reaches the highest eciency below 530 nm, and the wavelength dependence of the limiting
eect amplitude induced at a xed excitation wavelength increases monotonically to the
UV as expected from photo-induced scattering centers.
The time delay of the amplitude maximum and the uence threshold, where non-
linear eects are observed, dier for the time-resolved signals after nanosecond or
picosecond pulses [213]. Therefore, two types of scattering centers are successively
responsible for the optical limitation. The fast mechanism which reaches an amplitude
maximum in less than 1 nsec appears at relatively high uence (>0.94 J cm
2
, Fig. 20) and
with picosecond pulses, that is for high-energy connement. It is assigned to light
scattering by gold clusters that have expanded and vaporized after having absorbed an
important amount of light energy (Fig. 16). The slow limitation mechanism occurs in a
second step when the energy is transferred subsequently from the cluster to the solvent,
and is a result of light scattering by solvent bubbles. The second mechanism is observed
alone for 5-nm clusters even at high uences, or for 10- and 30-nm clusters at moderate
uences because the energy dissipation from small clusters into the solvent producing
bubbles is then more ecient and precludes metal particle vaporization.
Figure 17 Average diameter of gold nanoparticles after laser ablation at 532 nm and a laser
uence of (n) 320, (.) 480, and (x) 1200 mJ pulse
1
cm
2
as a function of the SDS concentration in
the solution. (From Ref. 208.)
The tests for limitation eciency as a function of the number of pulses (8 nsec, 5 J
cm
2
) have shown that the 10-nm clusters are irreversibly modied and lose their activity
after 20 pulses [213]. It was concluded that the limitation decrease is due to the decrease
after each pulse of the size of part of the clusters below the size threshold for optical
limitation. For 30-nmclusters, the condensation following the vaporization leads to smaller
clusters, but the size after relaxation is still large enough to cause optical limitation, and the
cluster is able to absorb again enough energy to vaporize. After 20 pulses, an equilibrium
size, with a two times lower eciency, seems to be reached.
8. CONCLUSION
Radiation chemical methods have been proven to have a potential to induce and to study
the dynamics of nucleation and growth and of the reactivity of metal clusters from the
monomer to the stable nanoparticle.
Pulse radiolysis permits the study, via the time-resolved technique, of the detailed
mechanisms of metal ion reduction in dierent environments (ligand, solvent, support, . . .),
Figure 18 Comparison of optical absorption data and TEM images (at the same magnication)
for two gold samples irradiated by laser pulses having the same uence (0.25 J cm
2
) and dierent
pulse width. Top: with a 7-nsec laser pulse at 800 nm. (a) Partial melting of the gold nanorods and
(b) selective optical hole burning in the near-IR band corresponding to the nanorods. Bottom: with
laser pulses of 100 fsec. (c) Complete melting of the gold nanorods into nanodots and (d) complete
depletion of the nanorod band. (From Ref. 211.)
of nucleation of atoms into oligomers, of their growth into stable metal clusters, and of the
reactivity of the transient species at each step, also in mixed solutions of two dierent metal
ions. Thus during this growth process, the nuclearity-dependent properties of oligomers
and clusters were determined, such as the redox potential, which is of crucial importance in
certain catalytic reactions and for the growth itself which can be autocatalyzed, and for the
stability of the clusters at the nal size.
Pulse radiolysis and pulsed laser methods are powerful tools to study the reactions at
the interface between clusters and solution, such as fast heterogeneous catalytic processes,
or transfer of the charges generated inside the particle.
The generation of clusters through irradiation of a homogeneous ionic solution has
numerous advantages: (1) an ideal instantaneous mixing of the radiolytic species, acting as
the reductant, with the ions; (2) the strong reducing properties of these species even at room
temperature and a formation of atoms without energetic barrier; (3) a strict control of the
reduction equivalents by the choice of the dose; (4) a control of the competition between the
creation of isolated atoms and the growth of nuclei by the choice of the dose rate from slow
to quasi-sudden regimes. The chances to create isolated atoms in the rst step are thus
Figure 19 Size dependence of the optical transmission obtained at 532 nm vs. the laser uence for
g-induced gold clusters. (.) 5-nm diameter (PVA 0.1 mol L
1
). (o): 10 nm diameter (PVA 10
3
mol
L
1
). (D): 30 nm diameter (PVA 0.1 mol L
1
, MV
2+
10
3
mol L
1
). (5): Reference solution
containing PVA and MV
2+
without clusters. TEM micrographs of the samples I, II, and III are on
the right. (From Ref. 213.)
higher than in any other method. (5) The possible synthesis in situ of clusters inside cavities
of opaque porous material. These conditions explain why the general concept of size eects
on cluster properties, which are the most drastic at low nuclearity, was indeed pointed out
rst in radiolytic experiments. They also explain that the growth can be restricted to very
small nal sizes and that their distribution is exceptionally narrow.
The knowledge of the kinetics mechanism, explaining the properties of the nal
particles from the conditions of the radiolytic synthesis, has been exploited for guiding the
procedure of obtaining clusters with denite size and composition according to the needs
of various studies and applications. Due to this mastering, an increasing number of data
have been obtained on the cluster size- and shape-dependent properties, such as optical
and magnetic properties, fusion temperature, cluster-to-solvent thermal energy transfer,
optical limitation, etc. The understanding of the detailed mechanism of bimetallic cluster
synthesis has also permitted the control of conditions favoring alloying, possibly with
ordered atom arrangement, or segregation in a coreshell structure. Moreover, except for
the reduction step, the mechanism is not specic to the radiation-induced method and will
be helpfully extended to other ways of chemical or photochemical synthesis. In photog-
raphy, this understanding resulted in a new interpretation of the critical nuclearity and
of the selective amplication occurring during the development. Besides, conditions were
Figure 20 Time proles of induced absorbance at 580 nm after focusing a 30-psec, 532-nm laser
pulse at various uences F onto gold clusters, 30 nm diameter. Dotted line: time prole of the pulse.
The fast amplitude increase, up to a maximum in less than 1 nsec for uences z0.9 J cm
2
, is
assigned to light scattering by expanded metal clusters. The delayed increase with a maximum at 3
nsec occurs at uences z0.18 J cm
2
already, and is assigned to light scattering by solvent bubbles.
(From Ref. 213.)
found of favoring the latent image formation and markedly enhancing the photographic
sensitivity by suppressing the electronhole recombination.
However, the variety of composite materials to be elaborated by the method is still
barely explored. For example, bi- and multimetallic nanoparticles, included in dierent
matrices (polymeric membranes, porous supports, . . .) or functionalized, have promising
applications. New methods of cluster characterization at this extremely low size scale are
developed and will improve their study.
Moreover, the interpretation of experimental data on clusters in solution requires
more elaborate theoretical models to include the solvation eects around the structure of a
small metal cluster. New kinetic models must be developed to describe nucleation, which
governs the phase transition from a solute to a small solid phase.
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21
Application of Radiation Chemical Reactions
to the Molecular Design of Functional
Organic Materials
Tsuneki Ichikawa
Hokkaido University, Sapporo, Japan
Although radiation chemical reactions have been applied to many industrial elds, espe-
cially to polymer industries, they are mainly aimed at improving the mechanical, thermal,
and surface properties of materials [1]. Applications of radiation chemical reactions to the
construction of modern functional organic materials such as electronic and optical materials
are relatively few. However, radiation chemical reactions have the following characteristics
that are advantageous for studying and constructing functional organic materials:
1. The reactions take place even in a solid without structural deformation, which is
advantageous for modifying the chemical and physical properties of precisely
shaped solid substances.
2. The reactions take place within the region where the radiation energy is absorbed,
so that only a part of a solid substance can be modied with precise spatial
resolution. Moreover, the region is controllable three dimensionally by changing
the eld of exposure and the depth of penetration that depends on the energy of
ionizing radiation.
3. The reactions can be induced without additives, which is advantageous for main-
taining the purity of materials.
In the following section, we will show how radiation chemical reactions are useful for the
molecular design of functional organic materials by taking our recent studies on next-
generation resist polymers and organic semiconductors as examples.
1. APPLICATION OF DISSOCIATIVE ELECTRON ATTACHMENT TO THE
CONSTRUCTION OF RADIATION RESIST
Because of their short wavelength, ionizing radiations such as ultra-short-wave UV light,
x-rays, and electron and ion beams have been considered to be the light sources of next-
generation lithography for mass production of very large scale integrated circuits [25].
The lithography process is based on radiation-induced change in the dissolution rate of
resist polymers. Ionizing radiation induces either degradation or cross-linking of resist
polymers, which increases or decreases the dissolution rate, respectively.
Poly(methyl methacrylate) (PMMA) has been widely used as a radiation-degradable
resist polymer [6]. Although PMMA has high spatial resolution of less than 10 nm, the
sensitivity to ionizing radiation is poor. Several attempts to increase the sensitivity have been
made by modifying the molecular structure of polymers [710]. However, the sensitivity is
still not enough for mass production. Another shortcoming is the limited spatial resolution.
The main chains of PMMA are randomly destroyed by homolytic scission [1113], so that
the molecular weight of the decomposed polymer has a wide distribution, which limits the
resolution if a spatial resolution of less than the original molecular size is expected.
A novel approach to increase the sensitivity and the spatial resolution is to use a
polymer that can be cut just in half by ionizing radiation. Because the selective scission of
the polymer skeleton does not leave a longer fragment that is dicult to be dissolved, the
sensitivity and the resolution are expected to be improved [14,15] by using such a polymer
as a radiation resist (see Fig. 1).
Dissociative electron attachment is a radiation chemical reaction suitable for cutting
a polymer just in half. If two equivalent polymer skeletons R are connected with a
functional group XY that has a large cross section of dissociative electron attachment, the
polymer captures an ejected electron at the center of the polymer skeleton and is broken
into two fragments with similar molecular weight, as RXYR + e
!RX
+ YR. The
key to construct such a polymer is to nd a functional group that is possible to connect
two polymer chains, to capture an electron eciently, and to dissociate into two fragments
after the capture.
1.1. Molecular Design for Position-Selective Scission of Polymer Skeleton
The dissociation of a functional group connecting two polymer skeletons must be fast
enough for competing the charge recombination due to the migration of positive charges.
Assuming the linear free energy relationship, a functional group with larger heat of dis-
sociative electron attachment is expected to have lower activation energy of dissociation.
Esters of carboxylic acids are strong candidates for the dissociative electron attachment,
Figure 1 Schematic representation of the formation of polymer fragments by random scission
(left) and selective scission by dissociative electron attachment (right).
since the dissociation of ester anions is expected to be easy due to high stability of resultant
carboxylate anions [16].
Table 1 shows molecular products generated by electron attachment to several esters
at 77 K in 2-methyltetrahydrofuran (MTHF) matrices. The concentration of the esters is
ca. 0.05 mol/dm
3
. Table 1 also shows the changes in enthalpies for the dissociation of anion
radicals into carboxylate anions and neutral free radicals that are calculated from the
experimental values of electron anities of carboxylates and the dissociation energies of
ester bonds [17]. Within the solutes examined, only benzyl esters dissociate into carboxylate
anions and benzyl radicals that show intense absorption and uorescence bands with
maxima at 320 and 475 nm [18], respectively (see Fig. 2). Dissociative electron attachment
to alkyl esters is endothermic, so that the electron attachment does not result in the dis-
sociation but simply gives their molecular radical anions with broad absorption bands at
<600 nm, which is attributable to ketyl-type anions with the unpaired electron on the
carbonyl carbon and the excess charge on the carbonyl oxygen [19]. Although the heat of
dissociative electron attachment is higher for C
2
H
5
COOCH
2
C
16
H
9
and CF
3
COOC
2
H
5
than
for C
2
H
5
COOCH
2
C
6
H
5
, as shown in Fig. 3, electron attachment to C
2
H
5
COOCH
2
C
16
H
9
and CF
3
COOC
2
H
5
give the radical anions showing the absorption spectrum very similar to
the pyrenyl radical anion [20] and the ketyl-type anion, respectively.
These results indicate that the dissociation of an ester radical anion into a carboxylate
anion and a neutral free radical is controlled by two factors. One is the exothermicity of the
reaction and the other is the distribution of the excess electron on the radical anion.
Dissociation of an ester radical anion takes place if the change in the free energy is negative.
Because the change in entropy is positive for the dissociation, the change in the free energy,
DG = DHTDS, is always negative if the change in the enthalpy is negative. However,
the negative change in the free energy does not certify the dissociation of the radical anion.
The radical anion does not dissociate if the activation energy for the dissociation is too high.
The activation energy is lowered if the radical anion of the ester R
1
COOR
2
shares the
excess electron with R
1
COO and R
2
groups, because the sharing causes the formation of
Table 1 Reaction of Free Electron with Esters in MTHF
Solute
Expected
reaction DH/kJmol
1
Observed
radical
a
Yield
of acid
b
C
6
H
5
COOCH
2
C
6
H
5
C
6
H
5
COO
+
CH
2
C
6
H
5
48 CH
2
C
6
H
5
f2.5
C
2
H
5
COOCH
2
C
6
H
5
C
2
H
5
COO
+
CH
2
C
6
H
5
17 CH
2
C
6
H
5
f2.5
C
11
H
23
COO
CH(C
6
H
5
)C
8
H
17
C
11
H
23
COO
+
CH(C
6
H
5
)C
8
H
17
17 CH (C
6
H
5
)C
8
H
17
f2.3
C
2
H
5
COOCH
2
C
16
H
9
C
2
H
5
COO
+
CH
2
C
16
H
9
52 [C
2
H
5
COOCH
2
C
16
H
9
]
<0.15
CF
3
COOC
2
H
5
CF
3
COO
+
C
2
H
5
50 [CF
3
COOC
2
H
5
]
<0.15
C
2
H
5
COOC
2
H
5
C
2
H
5
COO
+
C
2
H
5
57 [C
2
H
5
COOC
2
H
5
]
<0.15
C
2
H
5
COOC(CH
3
)
3
C
2
H
5
COO
+
C(CH
3
)
3
40 [C
2
H
5
COOC(CH
3
)
3
]
<0.15
a
In solid matrices at 77 K.
b
Number of molecules per 100 eV radiation energy absorbed to MTHF solution at 293 K.
an antibonding orbital on the ester bond and therefore the reduction of the activation energy
for the dissociation. However, because the electron anity of C
16
H
9
or CF
3
CO is much
higher than those of their counterparts, the radical anion of C
2
H
5
COOCH
2
C
16
H
9
or
CF
3
COOC
2
H
5
does not share the excess electron but is localized on C
16
H
9
or CF
3
CO,
respectively. The radical anion of C
2
H
5
COOCH
2
C
16
H
9
or CF
3
COOC
2
H
5
is therefore
stable. The excess electron on benzyl esters may occupy the antibonding orbital of the ester
Figure 2 Excitation (broken line, observed wavelength = 475 nm) and uorescence (solid line,
excitation wavelength = 320 nm) spectra of the benzyl radical generated in g-irradiated MTHF at 77
K by dissociative electron attachment to C
2
H
5
COOCH
2
C
6
H
5
.
Figure 3 Absorption spectra for g-irradiated MTHF at 77 K containing C
2
H
5
COOCH
2
C
16
H
9
(solid line) and CF
3
COOC
2
H
5
(broken line).
bond, so that the activation energy is low enough to dissociate into the carboxylate anion
and the benzyl radical even at 77 K (see Fig. 4).
Figure 5 shows the relationship between the concentration of benzyl esters and the
yield of benzyl radicals that is determined from the absorption band at 320 nm. The yield
is saturated at 0.03 mol/dm
3
, which indicates that 0.03 mol/dm
3
of benzyl esters capture
all electrons generated in MTHF and toluene matrices at 77 K. It turns out that one benzyl
ester molecule can capture an electron that is generated within the radius of 2.4 nm.
Assuming the molecular weight of one monomer unit to be 100, one benzyl ester in 333
monomer units is enough for collecting all electrons generated by ionizing radiation from
a polymer with the specic density of unity. The yield of benzyl radicals in toluene is
about one fth of that in MTHF, which is due to the protection eect of the aromatic
solvent; the yield of ejected electrons available for the dissociative electron is much lower
in toluene. Assuming that the G value (the number of events per 100 eV radiation energy
absorbed) of free-electron formation is 2.5, the radiation dose for reducing the initial
molecular weight of 33,300 to 16,650 is 120 kGy.
1.2. Synthesis of Polymer by Living Radical Polymerization
Since the benzyl esters are found to be a suitable functional group for connecting two poly-
mer skeletons, the next problem is to connect two equivalent polymer skeletons with benzyl
esters. This can be achieved by applying recently developed living radical polymerization
[2123].
Synthesis of polymer molecules with the same molecular weight necessitates living
polymerization. Although living polymerization in homogeneous systems had been limited
to ionic polymerization, recent development of polymer science makes it possible to
synthesize polymers with narrow polydispersity by radical polymerization. Living polymer-
ization necessitates propagating polymer ends that do not deactivate during the polymer-
ization. Regular radical polymerization is not living because the propagating radicals
quickly combine with each other. Living radical polymerization protects terminal radicals
from the combination by using a radical capping agent such as stable nitroxyl radicals.
Heating a mixture of monomer Mand a initiator RONXwith a capping agent ONXstarts
the dissociation of the initiator into reactive and stable free radicals, and therefore starts the
polymerization at about the same time, as
RONX
!
RONX; RM!RM:
The capping agent protects the deactivation of propagating radicals during the polymer-
ization, because the steady-state concentration of reactive propagating radicals is lowered
by the reaction with the capping agent.
Figure 4 Schematic representation of the molecular orbitals of an excess electron on dissociative
(left) and nondissociative (right) functional groups.
RM
n
ONX !
p
RM
n
ONX
There are two strategies for constructing a polymer with benzyl ester in the middle of
the skeleton. One is to make polymer skeletons with the same molecular weight, and then
combine two skeletons with benzyl ester. The other is to synthesize a chemical with
propagation sites of polymerization at both sides of benzyl ester, and use the chemical as
an initiator of living polymerization. Since the former strategy did not work well, probably
due to low reactivity of polymer molecules with benzyl esters, the latter approach will be
mentioned.
We synthesized polystyrene with benzyl ester in the middle of the skeleton by using
the following initiator that dissociates into stable tetramethylpyperidinoxyl radical and
reactive benzyl-type radical.
Figure 6 shows the results of the living radical polymerization of styrene at 400 K.
The linear dependence of the molecular weight on the conversion ratio and the narrow
distribution of the molecular weight are the evidence of living radical polymerization.
Figure 7 shows the proles of the size exclusion chromatography (SEC) of coupled
polystyrene that was dissolved in MTHF and irradiated at 295 K with a Co 60 g-ray
source. The irradiation cuts the main chains just in half, which indicates that the scission
of the skeleton exclusively takes place in the middle of the skeleton by dissociative electron
attachment to the benzyl ester. Figure 8 shows the distribution of the molecular weight of
polystyrene after g-irradiation at 295 K of MTHF solution containing 10 wt.% of coupled
polystyrene. The G value of the dissociation into two polymer fragments is about 5, which
is twice as much higher as that of corresponding C
6
H
5
COOCH
2
C
6
H
5
. The eciency of the
scission in toluene solution is about one fth of that in MTHF, which is due to the
protection eect of the aromatic solvent.
Figure 5 Relation between the radiation chemical yield of the benzyl radical and the concentration
of benzyl esters in 2-methyltetrahydrofuran and toluene at 77 K.
Figure 6 Relation between the conversion ratio and the molecular weight of coupled polystyrene
generated by living radical polymerization at 300 K.
Figure 7 Size exclusion chromatography proles of coupled polystyrene before and after g-irradia-
tion in MTHF at 295 K.
As shown in Fig. 9, irradiation of neat polystyrene does not result in the ecient scis-
sion but increases the molecular weight due mainly to cross-linking, though a small bump
at the low molecular weight side of the SEC pattern indicates the dissociative electron
attachment. The cross-linking is suppressed by addition of hydroquinone as a radical scav-
enger, which suggests that combination reaction of polymer radicals takes place in the neat
polymer, as
CH
2
CHC
6
H
5
!CH
2
CHC
6
H
5
; CH
2
CC
6
H
5
H
CH
2
CHC
6
H
5
!CH
2
CC
6
H
5
H
CH
2
CHC
6
H
5
H !CH
2
CC
6
H
5
H
2
e
COOCHCH
3
C
6
H
5
!COO
CHCH
3
C
6
H
5
CH
2
CC
6
H
5
CH
2
CC
6
H
5
!CH
2
CC
6
H
5
2
cross link
CH
2
CC
6
H
5
CHCH
3
C
6
H
5
!
CH
2
CC
6
H
5
CHCH
3
C
6
H
5
graft
The cross-linking and the grafting of the polymer radicals are suppressed by the addition of
hydroquinone, as
CH
2
C C
6
H
5
HOC
6
H
4
OH !CH
2
C CH
6
H
5
OC
6
H
4
OH
CHCH
3
C
6
H
5
HOC
6
H
4
OH !CH
2
CH
3
C
6
H
5
OC
6
H
4
OH
Although the irradiation of 200 kGy decomposes about 80% of polystyrene in toluene by
the dissociative electron attachment, the yield of the decomposition is only 20% for solid
toluene. Because of its low eciency of scission, the coupled polystyrene may not be a
polymer suitable as a radiation resist. However, the present study has shown that a polymer
that can be decomposed into two equivalent skeletons by ionizing radiation is possible to be
Figure 8 Distribution of the molecular weight of polystyrene after g-irradiation at 295 K of
MTHF solution containing 10 wt.% of coupled polystyrene.
constructed by living radical polymerization. Our preliminary study on polymethylacrylate
containing benzyl ester in a part of the main chain showed that the eciency of the scission
for the neat polymer was comparable to that of the coupled polystyrene in MTHF, though
the scission does not take place without benzyl ester.
2. MOLECULAR DESIGN OF POLYSILANE AS A CONDUCTIVE POLYMER
Polysilanes are j-conjugated polymers composed of SiSi skeletons and organic pendant
groups. They are insulators with lled intramolecular valence bands and empty intra-
molecular conduction bands. However, because of strong j conjugation, they have rather
narrow band gaps of less than 4 eV [24,25] and are converted to conductors by photo-
excitation or by doping electron donors or acceptors. Recently they have attracted much
attention because of their potential utility as one-dimensional conductors, nonlinear
optical materials, and electroluminescent materials [2628].
The optical and electronic functions of polysilanes owe to their delocalized highest
occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO)
that are occupied by holes and conduction electrons, respectively. The polymer does not
show high conductivity or optical nonlinearity if the electrons or holes are localized on a
small part of the polymer chain. To elucidate the structure of HOMO and LUMO is
therefore important for the molecular design of polysilanes as functional materials.
Analyses of the electronic and electron spin resonance (ESR) spectra of the radical
cation and anion of polysilanes make it possible to elucidate the structure of HOMO and
LUMO, because an unpaired electron in the radical anion or cation occupies HOMO or
LUMO, respectively. As schematically depicted in Fig. 10, the radical ions of polysilanes
show absorption bands in UV and near-IR regions [2931]. The former band corresponds
to intraband transitions between valence and conduction bands. The latter band corre-
sponds to transitions within the valence or the conduction band [32,33]. Because the near-
Figure 9 Comparison of the SEC proles of coupled polystyrene g-irradiated at 295 K in vacuum
without additive (left) and with 0.07 mol/kg of hydroquinone (right).
IR band is characteristic to the transition of a hole in the radical cation or a conduction
electron in the radical anion, analysis of the near-IR band gives useful information on the
structure of these charge carriers. Analysis of the ESR spectra of radical ions is also useful
for elucidating the electronic structure of the carriers. The ESR spectra give direct infor-
mation on the structure of charge carriers in HOMO and LUMO, because ESR transitions
take place between the spin sublevels of ground-state unpaired electrons.
The radiation chemical matrix isolation is a useful method for the spectroscopic study
of radical ions. In this method, a solution containing a small amount of solute molecules is
rapidly frozen to make a rigid solid matrix and is then irradiated at cryogenic temperature.
The radical ions of solute molecules generated by ionizing radiation are immobilized in the
matrix, so that the lifetime of otherwise unstable radical ions is long enough for precise
spectroscopic measurements. The radical anion of solute molecules is selectively obtained by
using ether or alcohol, RH, as a solvent
RHionizing radiation !RH
ionization of solvent molecule

RH
RH !RH
2
R formation of solvent radical by proton transfer
S solute e
!S
electron capture by solute molecule

The radical cation is similarly obtained by using a halogenated molecule as a solvent.
RX solvent molecule; X Cl or Br ionizing radiation !RX
RX !RX
dissociative electron attachment

RX
RX !RXRX
hole transfer
RX
S !RXS
hole transfer from solvent to solute

The advantage of this radiation chemical method is that the by-products of radical
ions are scarcely generated, because the direct decomposition of solute molecules by
ionizing radiation is negligible due to low solute concentration. Another advantage is that
the molecular orbitals of radical ions are scarcely disturbed by their counterpart ions,
because electrons or holes are captured by solute molecules after traveling more than 5 nm
from the point of ionization [34].
Figure 10 Schematic representation of the electronic and electron spin transitions of polysilane
and its radical ions.
The electronic structures of polysilane radical ions have also been studied by pulse
radiolysis of the liquid solution [3540]. However, due to short lifetime of the radical ions,
the measurement is limited to electronic absorption spectroscopy.
The bulk conduction in solid polysilane can be divided into intramolecular and inter-
molecular conductions. Intermolecular conduction is the migration of a charge in the poly-
mer skeleton, whereas intermolecular conduction is the charge migration between polymer
molecules. Both the fast intramolecular and intermolecular conductions are desirable as a
good conductive polymer. In the following section, we will showhowthe radiation chemical
matrix isolation method is useful for obtaining information crucial for the molecular design
of conductive polysilanes.
2.1. Intramolecular Conduction
Intramolecular conduction of polysilanes arises from j conjugation between adjacent SiSi
bonds. Because j orbitals are axially symmetric with respect to their SiSi bonds, HOMO
and LUMO are considered to be delocalized over a signicant part of the polymer skeleton
no matter whether the polymer skeleton is distorted or not. However, this is not necessarily
the case. Figure 11 shows the ESR spectra of the radical cations of permethyloligosilanes
[33]. The hexamethyldisilane radical cation shows 19 hyperne lines with the hyperne
coupling constant of 0.566 mT and the binominal intensity ratio. The ESR line width of
oligosilane radical cations decrease with increasing length of the SiSi main chain, which is
due to the reduction of hyperne interaction with methyl protons by the decrease of the spin
density on each monomer unit. The observed spectra are in good agreement with the simu-
lated ones that are obtained by using hyperne parameters estimated from the ESR spec-
Figure 11 Observed () and simulated (- - -) ESR spectra of permethyloligosilane radical cations
at 77 K in g-irradiated freon matrices. The simulations were carried out under the assumption that
an unpaired electron is delocalized over the entire SiSi chain.
trum of the hexamethyldisilane radical anion under the assumption that the unpaired
electrons are delocalized all over the main chains. The degree of delocalization on poly-
silanes is therefore possible to be estimated from the ESR line width.
Figure 12 compares the ESR spectra of the radical cations of silane dimers and their
polymeric analogues. The observed spectra of polysilane radical cations are reproducible
by using hyperne parameters of the corresponding dimer radical cations and by assuming
that the partial delocalization of the unpaired electron on only six Si atoms.
The localization of an unpaired electron on a part of the polymer skeleton is also
supported by the analysis of the near-IR absorption spectrum. Figure 13 shows the ab-
sorption spectra of permethyloligosilanes and poly(cyclohexylmethylsilane) radical cations
at 77 K. Decrease of the energy of the near-IRband with increasing the main-chain length of
oligosilanes is due to the increase of j conjugation length. The energy of the near-IRband is
expected to be zero for polysilanes with electrons delocalized all over the polymer chain,
because the energy levels composed of SiSi j orbitals become continuous. Observation of
the near-IR band around 0.8 eV therefore implies that the unpaired electron is not com-
pletely delocalized but is conned on a part of the polymer chain. The other polysilanes
such as poly(methylphenylsilane), poly(dibutylsilane), and poly(dihexylsilane) also show
the near-IRbands around 0.8 eV, which indicates that the HOMOof polysilanes is generally
localized on a part of the polymer skeleton.
Figure 12 Observed () and simulated (- - -) ESR spectra of disilane and polysilane radical cations
at 77 K in g-irradiated freon matrices. The simulation for polymers was carried out under the
assumption that an unpaired electron is localized on a part of polymer skeleton composed of about
six Si atoms.
As shown in Fig. 14, the energy of the near-IR band of the radical anions of permeth-
yloligosilanes also decreases with increasing main-chain length [32]. The near-IRabsorption
band of the radical anion of poly(cyclohexylmethylsilane) at around 0.8 eV indicates that
the unpaired electron is also localized on a part of the main chain composed of probably
six Si atoms. The degree of delocalization of an unpaired electron in the radical anion of
polysilanes cannot be estimated from the ESRline width, because the spectra scarcely show
the hyperne interaction with protons in the side chains. The solvatochromatic shift of
poly(cyclohexylmethylsilane) radical anion also supports the localization of the unpaired
electron [41]. Figure 15 shows the absorption spectra of the radical ions of poly(cyclohexyl-
methylsilane) in the mixed solvent of MTHFand methylcyclohexane at 77 K. Increase of the
concentration of polar MTHF in nonpolar methylcyclohexane causes the blue shift of the
near-IR band. Solvatochromic shift by polar solvents arises from the dierence of polar-
ization energies between ground and excited electronic states and is smaller for molecules
Figure 13 Absorption spectra of permethylorigosilane and poly(cyclohexylmethylsilane) radical
cations at 77 K in g-irradiated freon matrices.
Figure 14 Absorption spectra of permethylorigosilane and poly(cyclohexylmethylsilane) radical
anions at 77 K in g-irradiated MTHF matrices.
with diusive charge distribution. The observed solvatochromic shift proves that a negative
charge or an unpaired excess electron is conned on a part of the polymer skeleton, because
the solvatochromic shift is not expected for a polymer ion with the charge distribution over
the entire main chain. Analysis of the solvation structure for poly(cyclohexylmethylsilane)
radical anion by electron spinecho envelope modulation also indicates that the unpaired
electron is conned in a segment composed of six to eight Si atoms [42].
Understanding of the localization of unpaired electrons on a part of polymer
skeletons necessitates detailed knowledge about the structure of HOMO and LUMO.
As shown in Fig. 16, the intramolecular valence and conduction bands are composed of
bonding and antibonding SiSi j orbitals, respectively. The HOMO locating at the top of
the valence band is given by a linear combination of the bonding orbitals with alternating
phase. The atomic orbitals at Si atoms composing the HOMO are then expressed by
HOMO
1
2
p r
SiSi
sp
3
r
SiSi
sp
3
2
p
1
2
p 3p
x
1
2
3p
x
1
2
3s

2
p 3p
x
1
2
3p
y
1
2
3s

3p
x
1
where j
SiSi
(sp
3
) and j
SiSi
V
(sp
3
) denote hybrid orbitals composed of two adjacent SiSi
j bonds. The HOMO is composed of only Si 3p
x
atomic orbitals, so that this is a pseudo-k
orbital. The LUMO locating at the bottom of the conduction band is given by a linear
combination of the antibonding orbitals with the same phase, so that the atomic orbitals
for the LUMO are expressed by
LUMO
1
2
p r*
SiSi
sp
3
r*
SiSi
sp
3
2
p
1
2
p 3p
x
1
2
3p
y
1
2
3s

1
2
p 3p
x
1
2
3p
y
1
2
3s

2
p 3p
y
3s 2
Figure 15 Solvatochromic shift for poly(cyclohexylmethylsilane) radical anion in the mixed sol-
vent of MTHF and methylcyclohexane at 77 K.
where j*
SiSi
(sp
3
) and j*
SiSiV
(sp
3
) denote hybrid orbitals composing two adjacent anti-
bonding SiSi j* bonds. The LUMO is further coupled with SiC antibonding orbitals to
eliminate Si 3s orbital, since the ESR spectra of permethylorigosilane and polysilane
radical anions do not show
29
Si hyperne splitting arising from Fermi contact interaction
by an unpaired electron in the Si 3s orbital [32]. The actual atomic orbital for the LUMO
is therefore 3p
y
. The reason for mixing with SiC antibonding orbitals will be given in the
next section.
The delocalization of the HOMO and LUMO arises from pseudo-k orbital inter-
actions between adjacent 3p
x
and 3p
y
atomic orbitals of Si atoms, respectively. Since the 3p
orbital is on the SiSiSi plane, the degree of the interaction depends on the dihedral angle
between adjacent SiSiSi planes. Fluctuation of the dihedral angles along the polymer
skeleton then causes the so-called Anderson localization of the HOMO and LUMO [41].
Anderson localization is the localization of electrons on low-dimensional materials,
which is induced by the irregularity of the periodic potential eld [43]. Figure 17 gives a
schematic representation of Anderson localization of a particle in one-dimensional box. The
same is true for an electron on a polymer skeleton. Alocalized state in a completely periodic
Figure 16 Schematic representation of the HOMO and LUMO of polysilanes.
Figure 17 Schematic representation of Anderson localization of a particle in one-dimensional box.
eld is expressed by the superposition of steady-state delocalized wave functions of ground
and excited states, so that the energy of a localized state is always higher than that of the
delocalized ground state. Increase of the irregularity of the periodic eld causes the increase
of the ambiguity of the energies of delocalized states, which reduces the energy dierences
between the delocalized ground and excited states. The energy for generating a localized
state therefore decreases with increasing irregularity, and a localized state becomes a ground
state if the irregularity exceeds the energy gaps between adjacent delocalized states. In other
words, the irregularity of the potential energy eld allows the mixing of delocalized ground
and excited states to generate a localized ground state. The Anderson localization is easier
for a longer polymer skeleton, because the energy gaps between adjacent energy levels de-
crease with increasing length of the skeleton.
Anderson localization is dicult to take place for conformationally constrained
polymers with narrow distributions of dihedral angles. Introduction of bulky side chains is
therefore expected to enhance the delocalization of the HOMO and LUMO of polysilanes
[44]. Figure 18 shows the absorption spectra of the radical ions of poly(n-decyl-(S)-2-
methylbutylsilane) that is a rigid rodlike polysilane with narrow distribution of the
torsional angles [45,46]. The energy of the near-IR bands is much lower than that of
poly(cyclohexylmethylsilane), which indicates that the Anderson localization is suppressed
in poly(n-decyl-(S)-2-methylbutylsilane). The absorption spectrum of the radical anion of
poly(n-decyl-(S)-2-methylbutylsilane) in nonpolar methylcyclohexane matrix is the same as
that in polar MTHF. Observation of no solvatochromic shift also indicates the suppression
of the Anderson localization, because the solvatochromic shift is not expected for a
polymer ion with extended charge distribution.
The sharpness of the UV absorption and emission bands corresponding to HOMO X
LUMO transition is also a measure of delocalization. The transition energy depends on the
location of a polymer skeleton where a photon is absorbed or emitted, if electron orbitals are
localized on parts of the skeleton. A sharp UV band of poly(n-decyl-(S)-2-methylbutylsi-
lane) indicates the delocalization of HOMO and LUMO. Table 2 summarizes the location
Figure 18 Absorption spectra of poly(n-decyl-(S)-2-methylbutylsilane) at 295 K in MTHF and its
radical cation and anion at 77 K in g-irradiated freon and MTHF matrices, respectively.
and the width of the UV absorption and emission bands for several polysilanes. Polysilanes
with pendant groups composed of zC
6
linear alkanes and branched alkanes with the branch
at the h position show sharp UV bands and low Stokes shifts, which indicates that these
pendant groups are eective for stretching the polymer skeleton [47] and therefore for
preventing the Anderson localization.
The structures of polysilanes with exible and rigid skeletons are schematically shown
in Fig. 19 together with the distribution of charge carriers on the skeletons. In conclusion, to
replace the pendant groups of polysilanes with bulky ones is an eective way of suppressing
the undesired Anderson localization of charge carriers on a part of the polymer skeleton. An
ideal polysilane quantum wire with high intramolecular charge mobility can be synthesized
by using bulky pendant groups.
Table 2 Absorption and Emission Bands of Polysilanes in MTHF at 296 K
Absorption band
a
Emission band
a
Pendant groups M
n
/10
4
M
w
/10
4
k
max
Width Stokes shift Width
1-Methylpropyl, decyl 0.39 0.52 no peak
(S)-2-methylbutyl, decyl 67.2 94.1 3.84 0.10 0.05 0.12
2-Methylpropyl, decyl 1.61 3.15 3.88 0.10 0.05 0.15
2-Ethylbutyl, decyl 1.25 2.66 3.83 0.1 0.04 0.10
(2-Methylpropyl)
2
0.22 0.24 3.97 0.22 0.25 0.21
3-Methylpentyl, decyl 29.5 41.3 3.87 0.22 0.13 0.28
n-Butyl, decyl 1.74 7.53 3.91 0.45 0.29 0.24
2-Methylpropyl, methyl 8.93 18.8 4.21 0.62 0.5 0.28
2-Methylpropyl, ethyl 3.55 5.23 3.97 0.28 0.27 0.32
2-Methylpropyl, propyl 2.38 2.93 4.05 0.28 0.20 0.27
2-Methylpropyl, butyl 3.60 5.30 3.98 0.18 0.12 0.19
2-Methylpropyl, pentyl 0.76 4.72 3.92 0.14 0.07 0.17
2-Methylpropyl, hexyl 1.94 3.55 3.88 0.10 0.04 0.15
a
In electron volts.
Figure 19 Schematic representation of the molecular structures of exible polysilane with Ander-
son-localized charge carrier (upper) and rigid polysilane with delocalized charge carrier.
2.2. Intermolecular Migration of Charge Carriers
It has been established from conductivity measurements that thermally activated and eld-
assisted hole hopping is responsible for the charge transport in solid polysilanes [48,49].
The mobility of the hole is as high as 10
8
m
2
/V sec, while the mobility of the electron is a
few orders of magnitude lower. In this section, we will show the reason why only the hole
is mobile in polysilanes and how we can construct electron-conductive polysilanes.
It has been shown in the previous section that the structure of conduction electrons on
polysilane skeletons is essentially the same as that of holes. The suppression of electron
conduction is therefore attributable to low electron conductivity of side chains, because
interchain charge hoppings through the side chains are necessary for the migration of con-
duction electrons between polymer molecules [50]. Figure 20 compares the ESR spectra of
the radical anion and cation of poly(cyclohexyl methylsilane) and poly(methylphenylsilane)
in MTHF and freon mixture, respectively. The line width for the radical anions primarily
arises from the anisotropy of the ESR g factors. The two radical anions show the same g
factors, which indicates that the helical structures of the polymer skeletons are the same [51].
The spectrum of the radical cation is more than ve times broader than that of the radical
anion. This is caused by stronger hyperne interactions between the unpaired electron and
the protons of the side-chain alkyl groups. The stronger hyperne interaction arises fromthe
delocalization of the hole onto the alkyl substituents. The lack of a detectable hyperne
interaction in the polysilane radical anion suggests that the excess electron in the LUMO or
the intramolecular conduction band is not delocalized onto the side chains so that the side
chains act as good intermolecular insulators for the conduction electron. On the other hand,
since the hole is delocalized onto the side chains, it can migrate to an adjacent main chain via
the side chains.
The optical absorption spectra of polysilane radical ions also support the validity of
the above-mentioned mechanism of charge migration. Figure 21 compares the absorption
Figure 20 Comparison of the ESR spectra of radical cations and anions of poly(cyclohexylme-
thylsilane) and poly(methylphenylsilane) at 77 K in g-irradiated freon and MTHF matrices,
respectively.
spectra of the radical anion and cation of both poly(cyclohexylmethylsilane) and poly-
(methylphenylsilane). The near-IR band of the radical anion is scarcely inuenced by the
substitution of the side chains from the cyclohexyl group to the phenyl group. On the
other hand, the near-IR band of the radical cation is blue-shifted by the substitution. This
indicates that the unpaired electron of the radical anion is conned within the main chain,
whereas that of the radical cation is extended onto the side chains.
The delocalization of the conduction electron onto the side chains would be expected
if the pendant groups were replaced with more electrophilic substituents than the phenyl
group. However, this is not the case. Figure 22 shows the absorption spectrum of poly-
(methylnaphthylsilane) radical anion. The absorption spectrum is very similar to that of
the naphthalene radical anion, which implies that the unpaired electron is localized on the
pendant group. Increase of the electron anity of pendant groups does not necessarily
cause the delocalization.
Replacing all the pendant groups with aryl groups attains the delocalization of the
unpaired electron. Figure 23 compares the absorption spectra of the radical anions of poly-
(4-ethylphenyl-phenylsilane) and poly(dicyclohexylsilane) in MTHF at 77 K. Although the
molecular structures of these polysilanes are similar, the absorption spectra are dierent.
The absorption spectrum of the poly(dicyclohexylsilane) radical anions is similar to that of
Figure 21 Comparison of the electronic absorption spectra of poly(cyclohexylmethylsilane) and
poly(methylphenylsilane) radical anions and cations at 77 K in g-irradiated MTHF and freon
matrices, respectively.
the poly(cyclohexylmethylsilane) radical anion; the unpaired electron is conned within the
main chain. The poly(4-ethylphenylphenylsilane) radical anion shows a blue-shifted near-
IR band and several peaks in visible and near-IR regions. The blue shift and the peaks
strongly suggest that the unpaired electron is extended onto the pendant groups. Recent
studies on the electroluminescence of polysilanes revealed that poly(di-4-t-butylphenylsi-
lane) is electron conductive [52], which also supports the delocalization of conduction
electron onto the pendant groups. Table 3 summarizes the experimental results on the near-
Figure 22 Comparison of the electronic absorption spectra of poly(methylnaphthylsilane) and
naphthalene radical anions at 77 K in g-irradiated MTHF matrices.
Figure 23 Comparison of the electronic absorption spectra of poly(4-ethylphenyl-phenylsilane)
and poly(dicyclohexylsilane) radical anions at 77 K in g-irradiated MTHF matrices.
IR bands of polysilane radical anions and the location of conduction electrons. Except for
poly(diarylsilanes), the conduction electron is conned either in the skeleton or in one of the
pendant groups.
The dierence of the spatial distribution of the conduction electron and hole on poly-
silanes can be explained by taking the shapes of the molecular orbitals on the main and
side chains into account. Figure 24 shows HOMO and LUMO of the model compounds of
polysilanes obtained by semiempirical PM3 calculations. The HOMO of all the model
compounds is extended to both the SiSiSi skeletons and pendant groups. The LUMO of
SiHC
2
H
5
(SiH
3
)
2
, the model compound of poly(dialkylsilane), and SiHC
6
H
5
(SiH
3
)
2
, the
model compound of poly(methylphenylsilane), is not extended onto the pendant group.
The LUMOof SiHC
10
F
7
(SiH
3
)
2
, the model compound of poly(methylnaphthylsilane), is on
the pendant group but not on the skeleton. Although the LUMO+1 of SiHC
10
F
7
(SiH
3
)
2
has approximately the same energy as that of LUMO, it does not mix with LUMO but is
localized on the pendant group. These results indicate that the mixing of the LUMO of the
skeleton and the pendant group is very dicult.
The diculty of the mixing arises fromthe symmetry of the atomic orbitals of LUMO
on the skeleton with respect to molecular orbitals on the pendant group. Let us assume
orbital interactions between polymer skeletons and pendant groups are much weaker than
those within the skeletons and within the pendant groups. The molecular orbitals of poly-
silanes are then divided into three parts, a delocalized orbital on a polymer skeleton, a
delocalized orbital on a pendant group, and a localized orbital on an SiC bond. The entire
orbitals are reconstructed from these partial orbitals by treating orbital interactions be-
tween the skeletons and the pendant groups as perturbations. Figure 25 illustrates the
shape of the partial orbitals before and after the reconstruction. As shown in Fig. 15, the
atomic orbitals of the delocalized HOMO and LUMO on the Si skeleton are given by 3p
x
and 3p
y
3s=
2
p
, respectively. The atomic orbital on the SiC carbon of the delocalized
HOMOof alkyl or aryl groups is 2p
x
, so that the delocalized HOMO on the Si skeleton and
pendant groups are mixed with each other through k-type interactions with 3p
x
and 2p
x
Table 3 Near-IR Spectra and the Location of Conduction Electron on Polysilanes
Pendant 1 Pendant 2 E
a
(pendant 2)/eV
Near-IR
band/eV
Electron
location
Methyl Phenyl 1.15 0.8 Main chain
Methyl p-Fluorophenyl 0.89 0.8 Main chain
Methyl Triuorophenyl Triuorophenyl
anion
Pendant 2
Methyl 1-Naphthyl 0.19 Naphthalene
anion
Pendant 2
Phenyl 4-Ethylphenyl 1.17 1.1 Main and
side chains
Phenyl 4-Propylphenyl Approx. 1.1 1.1 Main and
side chains
Phenyl 4-tert-Butylphenyl 1.06 1.1 Main and
side chains
Cyclohexyl Cyclohexyl 0.8 Main chain
Cyclohexyl Methyl 0.8 Main chain
atomic orbitals. The delocalized HOMO on the Si skeleton does not mix with the SiC j
orbitals, because 3p
x
is orthogonal to the j orbitals.
The LUMO on the Si skeleton interacts not with the LUMO on pendant groups but
with SiC antibonding j orbitals. The atomic orbital of the LUMO, 3p
y
3s=
2
p
, is
divided into two sp
3
j orbitals with the symmetry axes pointed toward two SiC bonds, as
1
2
p 3p
y
3s

2
p
1
2
3p
y
2
p 3p
z
1
2
3s

1
2
3p
y
2
p 3p
z
1
2
3s

3
These orbitals completely overlap with two SiC antibonding orbitals, since the antibond-
ing orbitals are expressed by
1
2
p
1
2
3p
y
F
1
2
p 3p
z
1
2
3s

2
p carbon sp
3
4
The LUMO on the Si skeleton therefore mixes up with the antibonding orbitals to generate
3p
y
atomic orbitals, as
Figure 24 Isosurfaces at F0.02 of molecular orbitals of the model compounds of polysilanes ob-
tained by semiempirical PM3 calculation.
1
2
p
1
2
p 3p
y
3s

2
p
1
2
3p
y
2
p 3p
z
1
2
3s

2
p carbon sp
3

1
2
p
1
2
3p
y
2
p 3p
z
1
2
3s

2
p carbon sp
3

2
5
3p
y
1
2
carbon sp
3

1
carbon sp
3

2

The LUMOon the Si skeleton is impossible to be extended onto the pendant group because
the SiCantibonding orbital is orthogonal to the delocalized LUMOon the pendant group.
Observation of no Si 3s component on the ESRspectra of oligosilane and polysilane radical
anions [32] supports the conclusion that the LUMO on the Si skeleton is mixed with the
antibonding SiC j orbitals. The energy diagram for the orbital interactions is also shown
in Fig. 25.
Figure 25 Energy diagrams for orbital interactions between polysilane skeleton and pendant group.
HOMO
Si
, HOMO
p
and LUMO
Si
, LUMO
p
denote the HOMO and LUMO delocalized on the skele-
ton and a pendant group, respectively. j
Si-C
and j*
Si-C
are bonding and antibonding SiC j orbitals,
respectively.
The mechanism of orbital interactions mentioned above is not applicable if each
monomer unit of polysilanes has sucient electron anity and two pendant groups of the
monomer unit have approximately the same electron anity. The LUMO of polysilanes is
then regarded as a series of the LUMOs of monomer units that is perturbed by SiSi bonds.
The LUMO of the monomer unit has some electron density on the Si atom, since the
unpaired electron in the LUMO is delocalized over the two pendant groups with approxi-
mately the same electron density. Connection of the monomer units with SiSi bonds
therefore causes the delocalization of the LUMO on adjacent monomer units and therefore
on both the Si skeleton and pendant groups.
In conclusion, radiation chemical matrix isolation technique gives precise informa-
tion on the electronic structure of charge carriers, which is useful for the molecular design
of organic semiconductors as electronic and optical materials.
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22
Applications to Reaction Mechanism Studies
of Organic Systems
Tetsuro Majima
1. INTRODUCTION
1.1. Radical Ions and the Generation Methods
Radical cation and anion (M
+/
) generated fromone-electron oxidation and reduction are

short-lived species, as important intermediates, in chemistry, physics, and biology. The
formation and the reactivity of M
+/
have been extensively studied with various research

aspects [119]. M
+/
has essentially radical- and ion-type reactivities which are dierent

from free radicals and ions. Excitation of M
+/
can generate M
+/
in the excited state

(M
+
*
/
*), and the chemistry involving M
+
*
/
* is an interesting research subject [2035].

Many organic M
+/
can be generated at high concentration of 10

6
10
3
M from
electrochemical reactions and chemical oxidation by using one-electron oxidants. How-
ever, heterogeneous formation on the electrode and subsequent two-electron oxidation
are involved in the former oxidation, and the kinetic measurements is essentially not
possible in the latter oxidation. Therefore, both methods can be used for the generation of
M
+/
, but not for the kinetic study involving M
+/
. Photochemical reactions such as

photoinduced electron transfer (PET) and resonant two-photon ionization (RTPI) are
used to generate M
+/
and M
+
, respectively. Laser ash photolysis (LFP) is a useful
technique for the kinetic study involving M
+/
. However, generation of M
+/
in
solution by PET must be accompanied by ion pair formation, e.g., M
+/
, M
+
/anion,
etc. Because solvated electron (e
s
) is also generated together with M
+
in RTPI,
recombination of e
s
and M
+
decreases the yield of M
+
. Such accompanied species
inuence the transient behavior of M
+/
. Moreover, M is limited for PET and RTPI, in

which M should have appropriate character such as lower oxidation potential (E
ox
) and
strong absorption at the laser wavelength (k).
On the other hand, M
+
or M
can be selectively generated in radiation chemical

reactions of any M in solution via pulse radiolysis (PR) and g-radiolysis (g-R) techniques
[1,3641], which are used in the present study. Pulse radiolysis has been widely used for the
kinetic study involving M
+/
. Various processes, such as ionization, excitation, electron

transfer, solvation, relaxation, decomposition, etc., occur initially in the radiation chem-
ical reaction in solutions. Chemical species generated from the initial processes react with
M as a solute molecule to generate eectively and selectively M
+
, M
, or M in the triplet
excited state (
3
M*) at nsec100 Asec after an electron pulse (e
) depending on the solvent.

M
+
is generated during PR of M in alkylhalides such as 1,2-dichloreethane (DCE) or
butyl chloride (BC), M
, in basic solvents such as N,N-dimethylformamide (DMF),

hexamethylphosphoric triamide (HMPA), tetrahydrofuran (THF), and 2-methyltetrahy-
drofuran (MTHF), and
3
M*, in benzene. The established reaction mechanisms for gen-
eration of M
+/
are shown in Eqs. (16). Because electron and hole are trapped by DCE
and DMF, respectively, as stable species, the reactivities of M
+
and M
can be studied in
the time scale of nsec100 Asec.
DCE QDCE
s
1
DCE
M ! M
DCE 2
e
s
DCE ! CICH
2
CH
2
CI
3
DMF QDMF
s
4
e
s
M ! M
5
DMF
DMF ! DMF H
DMF H
6
Either M
+
or M
at 10
5
M is generated during PR as the only species absorbing
light in the visible and near-infrared (NIR) regions [4254]. Because free M
+
or M
can
be generated during PR, eects of counter ionic species and charge recombination are not
involved in the time scale of nsec100 Asec. Thus PR has been extensively used for the
kinetic study involving various M
+/
.
The g-R of glassy rigid matrix of degassed BC or MTHF solutions containing M at
77 K can generate M
+
or M
, respectively, as stable species [40,41]. This technique is

useful to measure the absorption spectra of M
+
or M
at 77 K, although the kinetic

study involving M
+
or M
, particularly bimolecular reactions M
+
or M
with other
molecules, cannot be carried out because of the rigid matrix.
Because M
+/
has strong absorption in the visible region, photoirradiation of M
+/
with hv at k tuned to the absorption generates M
+
*
/
*. The photochemical
transformation of M
+/
generated in glassy rigid matrix of BC or MTHF at 77 K can be

easily studied with the conventional absorption measurement [5563], while the transient
phenomena of M
+
*
/
*, including bimolecular reactions, can be carried out using the

PRLFP combined method.
1.2. Pulse Radiolysis and Pulse Radiolysis-Laser Flash Photolysis
Pulse radiolysis was performed using e
from a linear accelerator at Osaka University

[4248]. The e
has an energy of 28 MeV, single-pulse width of 8 nsec, dose of 0.7 kGy,

and a diameter of 0.4 cm. The probe beam for the transient absorption measurement
was obtained from a 450-W Xe lamp, sent into the sample solution with a perpendicular
intersection of the electron beam, and focused to a monochromator. The output of the
monochromator was monitored by a photomultiplier tube (PMT). The signal from the
PMT was recorded on a transient digitizer. The temperature of the sample solution was
controlled by circulating thermostated aqueous ethanol around the quartz sample cell.
Sample solution of M (5 10
3
10
1
M) was prepared in a 1 1 cm rectangular
Suprasil cell.
The PRLFP combined method was constructed by PR as the rst irradiation and
LFP as the second irradiation with delay times of 10 nsec to 2 Asec, controlled by a delay
generator. A laser ash at 532 nm (hv
532
) was obtained by using the second-harmonic
oscillation from a Nd:YAG laser (Quantel Model Brilliant), which was operated by a large
current pulsed-power supply, which was synchronized with e
. The single hv
532
has a
0.5-cm diameter, 5-nsec duration, 100 mJ, and an incident photon number of 1.4 10
18
pulse
1
cm
2
. The laser beam was directed in the opposite direction of the electron beam
through the sample solution. The laser beam intersected the electron beam at an angle of
20j. An almost collinear arrangement was used, such that the narrow laser beam passed
through the central part of the irradiated volume. Transient absorption was measured by
using the probe beam mentioned above. The PRLFP combined method at low temper-
atures over the range of 140300 Kwas performed in the cell that was mounted in a variable-
temperature liquid-nitrogen cryostat.
Transient uorescence was measured without the probe beam. Fluorescence from the
sample solution was collected with a 50-mmlens with focal length of 70 mmand was focused
into a quartz optical ber with diameter 250 mm and length of 10 m, which transported the
uorescence to a gated-multichannel/monochromatic spectrometer. The gate time of the
image intensier in the uorescence was set to be longer than 20 nsec, typically 50 nsec, to
eliminate the eect of the mode dispersion of the optical ber. The emission from the
sample was measured for e/hv
532
, e
, and hv
532
irradiations. Fluorescence spectra were
obtained by subtraction of the spectra for e
and hv
532
irradiations from that for e
/hv
532
irradiation to eliminate the Rayleigh and Raman scatterings and other emissions induced
by hv
532
irradiation. Because e
irradiation gave no emission except the Cherenkov radia-

tion, whose duration was the same as that of e
, emission from the Cherenkov radiation

was omitted with a proper delay time longer than 10 nsec. Fluorescence quantumyields (u
f
)
were determined by the comparison of the integrated uorescence intensity normalized by
(110
DO.D.532/d
), where DO.D.
532
is the optical density at 532 nm, and d is the optical path
length equal to the beam diameter of e
(7 mm), with that of a dilute cyclohexane solution

of zinc(II) tetraphenylporphyrin with B
f
= 0.03 as a standard.
1.3. gg-Radiolysis
g-Radiolysis (g-R) of DCEor BCsolutions, at a concentration of 1.0 10
2
M, was carried
out in a Pyrex tube with an inner diameter of 1.0 cmor in 1.5-mm-thick Suprasil cells cooled
in liquid nitrogen at 77 Kfor UVvis absorption measurements, respectively, using a
60
Co g
source (dose, 2.6 10
2
Gy) [4248]. Optical absorption spectra were taken by a spectro-
photometer and a multichannel photodetector. Sample solutions were degassed by freeze
pumpthaw cycles. The irradiated sample at 77 K was placed in a precooled quartz Dewar
vessel, and the absorption spectra were measured at 77 K. Warming of the irradiated sample
was performed as follows. Immediately after the liquid nitrogen was removed from the
vessel, the sample was again placed in the vessel and the absorption spectra were measured
with the MCPDevery 3 sec for 3 min during an increase in temperature up to 90 K, measured
using a thermocouple. Because it took only 10 msec to measure each spectrum with the
MPCD, the temperature was kept constant while measuring the spectrum. Photoirradiation
of solutions after g-R was carried out in the vessel with a 150-W Xe lamp through a glass
lter (UV-39) at 77 K.
Product analysis of g-R was carried out in a Pyrex tube with an inner diameter of 1.0
cm at room temperature (r.t.). After g-R, the reaction mixtures were directly analyzed by
GC and GC-MS. The G values were calculated from the product yields, and the absorbed
dose measured by the ferrous sulfate dosimeter (Fricke dosimeter).
2. REACTIONS OF RADICAL CATIONS
2.1. Isomerization, Oxidation, and Dimerization of Radical Cations
of Stilbene Derivatives
Numerous studies on the reactions of radical cations of aromatic olens (ArO
+
) have been
reported from the synthetic and mechanistic points of view [1,2,4,8,42,6470]. It is well
known that cis(c)trans(t) isomerization, dimerization, and addition of a nucleophile occur
in ArO
+
as typical reactions [1,2,4,8,42,6470]. The reactivities depend on the structure or
substituents of ArO
+
. No unimolecular ct isomerization occurs in stilbene
+
(St
+
) [64
66], although it does so in c-4,4V-dibromostilbene
+
and c-4,4V-dimethylstilbene
+
[66].
Dimerization of St
+
with St occurs at k
d
= (3.53.9) 10
8
M
1
sec
1
[42,67] to yield k-
dimer
+
(k-St
2
+
) with overlapping k-electrons between the two benzene rings, which
converts to j-dimer
+
(j-St
2
+
) with an acyclic linear structure having both a radical and a
cation on the 1- and 4-positions of the C
4
linkage, decomposing to t-St
+
and St as nal
products [42]. Although t-St
+
has little reactivity toward O
2
, a high reactivity of k
O
2
=2.6
10
8
M
1
sec
1
has been reported for (E)-2,3-diphenyl-2-butene
+
[70].
Three reactions of eight stilbene derivatives
+
(S
+
= RCH j CRVRU = 1
+
8
+
)
(Scheme 1), unimolecular isomerization from c-S
+
to t-S
+
[Eq. (7)], and bimolecular
reactions with O
2
[oxidation, Eq. (8)] and a neutral S [dimerization, Eq. (9)] during PR and
g-R in DCE or BC will be described here [44,45,71].
c S
! t S
; k
i
for c t unimolecular isomerization 7
S
O
2
! RC
HCOO
CRVRVV; k
O
2
for oxidation 8
S
S ! S
2
; k
d
for dimerization 9
Scheme 1 Eight stilbene derivatives (S).
Formation and Reactions of c-S
+
and t-S
+
It is well established that 1
+
is formed during PR and g-R in alkyl halide such as DCE and
BC[40,7274]. The absorption spectra of c-S
+
and t-S
+
(S
+
=1
+
8
+
) generated by g-
Rof c-S and t-S in BCat 77 Kshowbands similar to those of c-1
+
and t-1
+
. The transient
absorption spectra immediately after e
were assigned to c-1
+
7
+
and t-1
+
8
+
[40,72,73], formed from capture of the hole generated in the initiation step during PR of S
in DCE (Figs. 1 and 2, Table 1). It is well known that t-1
+
shows two bands at 480 and
750 nm assigned to D
2
pD
0
and D
1
pD
0
transitions, respectively, while c-1
+
also shows
two bands at 515 and 780 nm, respectively [40,72,73]. The absorption bands of c-1
+
are
broader and weaker than those of t-1
+
. Delocalization of k-electrons is less in c-1
+
than
in t-1
+
.
The transient absorptions of t-S
+
decayed monotonously with rst-order kinetics
and did not show any shifts or spectral changes. The transient absorptions of c-1
+
, c-2
+
,
and c-6
+
without p-methoxyl group ( p-MeO) decayed with k
obs
, in a similar way to those
of t-1
+
8
+
. On the other hand, formation of the band of t-3
+
5
+
and t-8
+
after e
was observed with decay of the band of c-3
+
5
+
and c-8
+
with p-MeO, respectively. k
i
= 4.5 10
6
to 1.4 10
7
sec
1
for the unimolecular was isomerization of c-S
+
to t-S
+
was calculated from the rise of the peaks of t
+
, which did not depend on [c-S].
Dimerization was observed in 1
+
3
+
and t-6
+
, because the decay of the absorp-
tion of 1
+
3
+
and t-6
+
increased with increasing [S], respectively. The transient
absorption of c-1
+
shifted to that of t-1
+
during the decay because of the bimolecular
isomerization of c-1
+
to t-1
+
via j-1
2
+
. Similarly, the transient absorption of c-2
+
shifted to that of t-2
+
through bimolecular isomerization. k
d
= (2.04.3) 10
8
M
1
sec
1
were calculated from the dependence of k
obs
on [S] (Table 2). No dimerization of c-6
+
was
observed, because k
obs
did not depend on [c-6]. The transient absorption of c-7
+
with p-
MeO and methyl group (Me) on the olenic carbon decayed with k
obs
according to rst-
order kinetics without any shifts or dependence of [c-7]. In other words, neither unim-
olecular isomerization nor dimerization was observed in c-7
+
.
The k
obs
of t-S
+
(S =3
+
5
+
and 7
+
) with p-MeOwas accelerated in the presence
of O
2
, and k
O
2
= (1.24.5) 10
7
M
1
sec
1
for the oxidation was calculated (Table 2). On
the other hand, no oxidation was observed on a similar time scale in t-1
+
, t-2
+
, and t-6
+
without p-MeO nor in t-8
+
with two p-MeOs. Oxidation of c-7
+
was also observed with
k
O
2
similar to that for t-7
+
, while no oxidation was observed in c-1
+
, c-2
+
, and c-6
+
without p-MeO and in c-8
+
with two p-MeOs. In the case of c-3
+
5
+
with p-MeO,
k
O
2
could not be estimated because of the fast unimolecular isomerization of c-3
+
5
+
to
t-3
+
5
+
at k
i
= 4.5 10
6
1.3 10
7
M
1
sec
1
.
Dimerization Mechanism of c-S
+
and t-S
+
Decay of c-1
+
has been analyzed by neutralization with Cl
formed from dissociative

electron attachment to DCE [Eq. (3)] at k
n
= 1.6 10
11
M
1
sec
1
[Eq. (10)] when [c-1] is
low(10
4
M) [42,74]. It is reported that the dimerization of c-1
+
with c-1 occurs at k
d
c
=3.5
10
8
M
1
sec
1
at r.t. to formthe k-type dimer
+
of c-1 [k-(c-1)
2
+
, Eq. (11)], which changes
to j-type dimer
+
of 1 [j-1
2
+
, Eq. (12)] [42]. Such fast formation of j-1
2
+
was conrmed by
absorption measurement during g-R of c-1 in BC rigid matrix at 77 K(see Section 2.2). The
unimolecular isomerization of c-1
+
to t-1
+
does not occur, although the bimolecular
isomerization of c-1
+
to t-1
+
is proposed to occur through j-1
2
+
on the time scale of
100300 nsec at (510) 10
3
M at r.t. [42,67]. Thermally unstable j-1
2
+
decomposes
Figure 1 Transient absorption spectra of c-S
+
and t-S
+
(S
+
=1
+
4
+
) recorded at time t after
e
during PR of c-S and t-S (S = 14) with [S] = 5.0 10

3
M in DCE at r.t. Insets: kinetic traces
illustrating the time proles of the D
2
band at k as a function of t. Both t and the observed decay rate
constant (k
obs
) and k
i
are mentioned in the gure.
Figure 2 Transient absorption spectra of c-S
+
and t-S
+
(S
+
= 5
+
8
+
) recorded at time t after
e
during PR of c-S and t-S (S = 58) with [S] = 5.0 10

3
M in DCE at r.t. Insets: kinetic traces
illustrating time proles of the D
2
band at k as a function of t. Both t and the observed decay rate
constant (k
obs
) and k
i
are mentioned in the gure.
Table 1 Transient Absorption Peaks (k
max
) and the Molar Absorption Coecients at the Peak (e
k
)
of D
1
and D
2
of c-S
+
and t-S
+
(S
+
=1
+
8
+
) Obtained by Pulse Radiolysis (PR) of c-S
and t-S (S=18) (5.010
3
M) in 1,2-Dichloroethane (DCE) at r.t.
a
k
max
[nm] (e
k
[M
1
cm
1
])
S
+
c-S
+
(D
2
) t-S
+
(D
2
) c-S
+
(D
1
) t-S
+
(D
1
)
1
+
515 480 780 750
(180,000) (65,000) (6,180) (11,400)
2
+
520 490 780 790
(30,900) (80,900) (11,500) (19,600)
3
+
530 470,500 nd 720,800
(13,200) (39,200; 74,800) (14,700; 41,700)
4
+
530 480 nd 680
(nd) (105,000) (14,700)
5
+
540 480 nd 700
(nd) (84,600) (14,700)
6
+
520 460,510 700 >900
(3,270) (24,500; 208,000) (1,240) (>11,000)
7
+
450,500 440,490 760,780 740,800
(8,820; 9,710) (18,400; 29,400) (7,940; 7,940) (9,810; 184,000)
8
+
nd 480,540 nd 780,880
(33,100; 76,000) (24,500; 61,300)
a
e
k
was estimated from DO.D.
E
and the optical length of 1 cm with the assumption of [S
+
] = 8 10
6
M which
was calculated from DO.D.
480
, the optical length of 1 cm, and e
480
= 6.5 10
4
M
1
cm
1
for 1
+
in DCE.
Table 2 Rate Constants for the Reactions of S
+
(S
+
=1
+
8
+
) During PR in DCE at r.t.
a
S
+
c-S
+
t-S
+
k
i
[sec
1
] k
d
[M
1
sec
1
] k
o
2
[M
1
sec
1
] k
d
[M
1
sec
1
] k
o
2
[M
1
sec
1
]
1
+
<10
6
3.9 10
8
<10
6
3.9 10
8
<10
6
2
+
<10
8
3.4 10
8
<10
6
4.3 10
8
<10
6
3
+
4.5 10
6
2.0 10
8
nd 3.0 10
8
4.5 10
7
4
+
1.3 10
7
nd nd <10
6
4.0 10
7
5
+
1.4 10
7
nd nd <10
6
1.2 10
7
6
+
<10
6
<10
6
<10
6
3.410
8
<10
6
7
+
<10
6
<10
6
2.5 10
7
<10
6
2.8 10
7
8
+
nd nd <10
6
<10
6
<10
6
a
k
i
, calculated from the formation of t-S
+
at 5.010
3
M of c-S; k
d
, measured from the dependence of the decay
of S
+
on [S]; k
O
2
, obtained from the dependence of the decay of c-S
+
or t-S
+
on [O
2
]. k
i
<10
6
sec
1
denotes
that the formation of t-S
+
was not observed. k
d
<10
6
M
1
sec
1
and k
O
2
<10
6
M
1
sec
1
denote that there was
no dependence of the decay of c-S
+
or t-S
+
on [c-S], [t-S], or [O
2
].
rapidly into the thermodynamically stable t-1
+
and t-1 [Eq. (13)], as proposed [42,67].
Therefore the bimolecular isomerization is enhanced with increasing [c-1].
S
Cl
! neutral products; k
n
for neutralization 10
c S
c S ! p c S
2
S 1 3; k
c
d
11
p c S
2
! r S
2
12
r S
2
! t S
t S 13
Concentration eects suggest that the bimolecular isomerization of c-2
+
and c-3
+
to t-2
+
and t-3
+
involve the dimerization of c-2
+
and c-3
+
to form k-(c-2)
2
+
and k-
(c-3)
2
+
and then j-2
2
+
and j-3
2
+
[Eqs. (11) and (12), respectively]. Similar k
d
c
for c-1
+
c-
3
+
indicates that p-Me and p-MeO substitutions have little eect on the dimerization of
c-S
+
. Decay of the absorption of other c-S
+
at higher [c-S] could not be detected, because
the decay was too fast to be detected within the experimental limits, or [c-48] could not be
increased because of low solubilities in DCE. k
d
c
for c-8
+
with p-MeO is expected to be 10
8
M
1
sec
1
from analogy with c-3
+
, while the steric hindrance resulting from the twisted
structure with the 3,5-dimethoxyphenyl ring rotating relative to the CjC double bond
and to Me on the olenic carbon probably inhibits the dimerization of c-6
+
and 7
+
,
respectively.
Similarly to c-1
+
, t-1
+
decays via neutralization with Cl
[Eq. (10)] and dimerization

with t-1 at k
d
l
=3.9 10
8
M
1
sec
1
to formthe k-type dimer
+
of t-1 [k(t1)
2
+
, Eq. (14)]
with overlapping of k-electrons between the two benzene rings of t-1
+
and t-1.
3d,11
Neither
the unimolecular nor the bimolecular isomerization of t-1
+
to c-1
+
occurs. It is found that
k-(t-1)
2
+
generated at 77 K converts to j-1
2
+
upon warming [Eq. (15)], and nally de-
composes into the thermodynamically stable t-1
+
and t-1 [Eq. (13)] as discussed above for
c-1
+
[42].
t S
c S ! p t S
2
S 1 3; k
d
V 14
p t S
2
! r S
2
15
t-2
+
, t-3
+
, and t-6
+
show behavior similar to that of t-1
+
(Table 2). Similar k
d
1
for t-1
+
t-3
+
and t-6
+
suggests that p-Me and m-MeO substitutions have little eect on
dimerization of t-S
+
and the similar dimerization mechanism [Eqs. (1113)]. On the other
hand, k
obs
of t-4
+
, t-5
+
, t-7
+
, and t-8
+
were much slower than those of t-1
+
3
+
and
t-6
+
because k
obs
did not change with varying concentration (5 10
3
10
1
M). This
indicates that no dimerization of t-4
+
, t-5
+
, t-7
+
, and t-8
+
occurs. It is suggested that
the dimerization involves the initial formation of k-complex with overlapping of the two
benzene rings and that the k-complex formation is inhibited by steric hindrance of the
substituents on the benzene rings and olenic carbons.
Enhancements of Unimolecular Isomerization and Oxidation by ChargeSpin
Separation
In contrast to c-1
+
and 2
+
, the unimolecular isomerization of c-3
+
5
+
and c-8
+
having
p-MeO occurs to yield t-3
+
5
+
and t-8
+
, respectively, k
i
for c-4
+
and c-5
+
are larger
than those for c-3
+
and c-8
+
. Neither the unimolecular nor bimolecular isomerization
occurs in c-6
+
and c-7
+
. The oxidation of t-3
+
5
+
and 7
+
having p-MeO with O
2
occurs at k
O
2
= (1.24.5) 10
7
M
1
sec
1
, while no oxidation occurs in c-1
+
, c-2
+
, or
c-6
+
without p-MeO and in t-8
+
with two p-MeOs. The unimolecular isomerization and
oxidation with O
2
are remarkably enhanced in 3
+
5
+
and 7
+
with p-MeOas an electron-
donating substituent on the benzene ring.
It is reported that t-1
+
has a planar structure with two benzene rings and a CjC
double bond as the most stable conformation, while c-1
+
has a twist angle of 26j between
the two benzene rings on the basis of MOcalculations [75]. Although the positive charge and
unpaired electron are delocalized on the SOMO involving k-orbital of sp
2
C atoms and
n-orbital of O atom of p-MeO in 1
+
8
+
, as shown in structure (A), a quinoid-type
structure (B) is considered to contribute in 3
+
5
+
, 7
+
, and 8
+
with p-MeO but not in
1
+
, 2
+
, and 6
+
without p-MeO (Scheme 2). Alternatively, the n-orbital of O atom of
the p-MeO and the k-orbital of the olenic h-carbon participate considerably in the SOMO
of 3
+
5
+
, 7
+
, and 8
+
. Therefore, it is suggested that p-MeO in 3
+
5
+
, 7
+
, and 8
+
causes separation and localization of the positive charge on O atom of the p-MeO and an
unpaired electron on the olenic h-carbon (chargespin separation), which induces a twisted
conformation with a large twist angle and CUC single-bond character for the central CjC
double bond in (B). Such chargespin separation is less important in 1
+
, 2
+
, and 6
+
than
in 3
+
5
+
, 7
+
, and 8
+
. It is suggested that distonic radical cations known in the gas phase
[76] can be used to explain the reactivities of radical cations even in solution [77].
Neither the unimolecular isomerization of c-7
+
nor the oxidation of t-8
+
occurred,
although 7
+
and 8
+
have p-MeO. These are possibly explained in terms of a barrier to the
twisting of the CjC double bond and the spin density on the olenic carbon, respectively.
The contribution of (B) is decreased by the electron-donating Me on the olenic carbon;
therefore, it is suggested that the single-bond character of the CjC double bond is lower
in c-7
+
than in c-3
+
and that the barrier to the twisting of the CjCdouble bond is higher
in c-7
+
than in c-3
+
. An unpaired electron appears on the olenic carbon on the side of
the p-MeOin 3
+
because of contribution of (B), while it appears on both olenic carbons in
Scheme 2 Chargespin delocalization (A) and separation (B) in S
+
.
8
+
with two symmetrical p-MeOs. Therefore, the density of an unpaired electron on the
olenic carbon in t-8
+
is lower than that in t-3
+
. Neither the unimolecular ct isomer-
ization nor the oxidation of c-6
+
with an extremely small molar absorption coecient (e) at
k
max
, but similar to that of 1,3-dimethoxybenzene
+
[78] may be interpreted by a twisted
structure with the 3,5-dimethoxyphenyl ring rotating relative to the CjC double bond,
because (B), having m-MeO, is not possible in c-6
+
.
The k
i
for c-8
+
was measured at various temperature. Fromthe Arrhenius plot of ln k
i
and the reciprocal of the temperature (T
1
), the activation energy (E
a
) and the pre-
exponential factor (A) were determined to be 1.3 kcal mol
1
and 10
7.5
sec
1
, respectively,
which are smaller than E
a
= 7.7 kcal mol
1
and A = 10
11F2
sec
1
for c-4,4V-
dibromostilbene
+
and E
a
= 3.3 kcal mol
1
and A = 10
9F2
sec
1
for c-4,4V-
dimethylstilbene
+
[66]. This result is consistent with the larger k
i
for c-8
+
than for c-
4,4V-dibromo- and c-4,4V-dimethylstilbene
+
, and suggests that E
a
predominantly controls
the isomerization. Based on the dierences in E
ox
between c-S and t-S (Table 3), E
a
is too
high to be overcome in the isomerization of t-S
+
to c-S
+
(1114 kcal mol
1
). This renders
the isomerization one-way from c-S
+
to t-S
+
for S=16.
The k
O
2
for free radical-O
2
reactions is found to be nearly equal to the diusion rate
constant (k
di
). For example, k
O
2
=2.4 10
9
M
1
sec
1
for the benzyl radical-O
2
reaction is
similar to k
di
= 6.7 10
9
M
1
sec
1
in cyclohexane. On the other hand, k
O
2
= (1.24.5)
10
7
M
1
sec
1
for the oxidation of t-3
+
5
+
and t-7
+
are found to be two orders of
magnitude smaller than k
O
2
for free radicals and k
di
= 7.8 10
9
M
1
sec
1
in DCE.
This suggests that an unpaired electron is not completely localized on the olenic carbon in
t-3
+
5
+
and t-7
+
, and that the positive charge interferes with the reactivity of t-3
+
5
+
and t-7
+
as a radical toward O
2
because of the electrophilic character of O
2
.
Chain Isomerization and Oxidation of S
+
In order to conrm the enhancement of ct isomerization and oxidation by chargespin
separation in S
+
with p-MeO, product analyses were carried out. Isomerization from c-S
to t-S was found to occur stoichiometrically with large G values (5121) and G
lim
(2010
4
)
in g-R of c-S in DCE at r.t. (Table 4). The larger G values for the yield of t-35 and t-8
during g-R of c-35 and c-8, respectively, with p-MeO than for c-1, 2, and 6 without p-
MeO suggest a smaller barrier to ct isomerization for c-3
+
5
+
and c-8
+
than for c-1
+
, 2
+
, and 6
+
because of the greater single bond character of the former central CjC
double bond for c-3
+
5
+
and 8
+
relative to c-1
+
, 2
+
, and 6
+
because of the con-
Table 3 Half-Peak Oxidation Potentials (E
1/2
ox
) of c-S and t-S (S=16) and Dierence
Between E
1/2
ox
(c-S) and E
1/2
ox
(t-S)
a
S R of RCHjCHPh E
1/2
ox
(c-S)[V] E
1/2
ox
(t-S)[V] DE
1/2
ox
(c-t)[V]
1 Ph 1.25 1.14 0.11
2 4-CH
3
C
6
H
4
1.16 1.05 0.11
3 4-CH
3
OC
6
H
4
0.94 0.82 0.12
4 2,4-(CH
3
O)
2
C
6
H
3
0.80 0.64 0.16
5 3,4-(CH
3
O)
2
C
6
H
3
0.87 0.72 0.15
6 3,5-(CH
3
O)
2
C
6
H
3
1.23 1.03 0.20
a
E
1/2
ox
(c-S) and E
1/2
ox
(t-S) of c-S and t-S at 1.0 10
2
M, reference electrode of Ag/AgNO
3
, supporting electro-
lyte of 10
1
M tetraethylammonium tetrauoroborate in acetonitrile; DE
1/2
ox
(c-t) = E
1/2
ox
(c-S)-E
1/2
ox
(t-S).
tribution of (B) with separation and localization of the positive charge on O atom of p-
MeO and an unpaired electron on the h-olenic carbon (Scheme 2). The isomerization of
c-35 and c-8 proceeds via a chain reaction mechanism involving ct unimolecular
isomerization and endergonic hole transfer (HT) from t-S
+
to c-S. On the other hand,
the isomerization of c-1 and -2 proceeds via a chain reaction mechanism involving
dimerization and decomposition into t-S
+
and t-S.
The formation of oxidation products ac in a range of Gvalues (0.73.8) during the g-
R of S in O
2
-saturated DCE suggests that ac would be produced from complicated
reactions of peroxy radicals with S(Table 5). On the other hand, the regioselective formation
of 3d with large G values (2.63.0) in oxidation of 3
+
with O
2
is explained by spin
localization on the h-olenic carbon because of the contribution of (B) in 3
+
. The results of
products analyses are essentially identical with prediction based on k
i
and k
O
2
for S
+
measured with PR. It should be emphasized that the reactivities of ct unimolecular
isomerization and reaction of S
+
with O
2
can be understood in terms of chargespin
separation induced by p-MeO.
In conclusion, c-3
+
5
+
and c-8
+
with p-MeO generated during PR or g-R
isomerize unimolecularly to the corresponding t-S
+
at k
i
= 4.5 10
6
1.4 10
7
sec
1
,
while t-3
+
5
+
and 7
+
with p-MeO are oxidized with O
2
at k
O
2
= (1.24.5) 10
7
M
1
sec
1
. On the other hand, neither the unimolecular isomerization from t-S
+
to c-S
+
nor
the oxidation with O
2
occurs in t-S
+
without p-MeO. It should be noted that an unpaired
electron is not completely localized on the olenic carbon in t-3
+
5
+
and 7
+
and that a
positive charge interferes the reactivity of t-3
+
5
+
and 7
+
as a radical toward O
2
because of the electrophilic character of O
2
.
2.2. Cycloreversion of Tetraphenylcyclobutane Radical Cations (TPCB
+
)
Cleavage of a CUC bond gives a distonic radical cation as an intermediate, while concerted
cleavage of two CUC bonds yields the corresponding ArO
+
and ArO in cycloreversion of
aryl-substituted cyclobutane
+
. Therefore, the cycloreversion mechanism is related to
dimerization of ArO
+
, where k- and j-dimers
+
are detected during PR of ArO such as
Table 4 Products From g-Radiolysis (g-R) of c-S (S=18)
a
and k
i
of c-S
+b
Product from g-R
S Conv. of c-S [%] Yield of t-S [%] G-value of t-S G
lim
k
i
[sec
1
]
1 6.0 94 18.9 30 <10
6
2 5.4 100 18.2 200 <10
6
3 32.5 76 81.5 >10
3
4.510
6
4 26.0 100 105.6 >10
4
1.310
7
5 22.7 97 94.7 >410
3
1.410
7
6 2.9 100 10.2 140 <10
6
7 2.0 85 5.4 20 <10
6
8 39.1 100 120.6 >10
4
5.510
6
a
Dose, 2.610
2
Gy; [S] = 1.0 10
2
M in DCE; r.t.; the yield of t-S based on conversion of c-S; G value of t-S,
the yield of t-S; G
lim
, the G value of t-S at [c-S]
l
in the plots of G
1
of t-S vs. [c-S]
-1
.
b
k
i
, calculated from the formation of t-S
+
during PR of c-S at 5.0 10
3
M in DCE.
Table 5 Products From g-R of S (S=18) in the Presence of O
2
a
and k
O
2
of S
+b
RCHjCRVPh G value or yield
S R RV PhCHO a RCHO b RCH[O]CHPh
c
c RCH
2
C(jO)Ph
d
d k
O
2
[M
1
sec
1
]
c-1 Ph H 1.7 0.9 0.1 <10
6
t-1 Ph H 1.6 1.1 0.3 <10
6
t-2 4-CH
3
C
6
H
4
H 1.1 1.3 0.7 0.05 <10
6
c-3 4-CH
3
OC
6
H
4
H 1.0 1.6 1.2 3.0 nd
t-3 4-CH
3
OC
6
H
4
H 0.9 1.4 1.4 2.6 4.5 10
7
t-4 2,4-(CH
3
O)
2
C
6
H
3
H 1.3 1.5 nd nd 4.0 10
7
t-5 3,4-(CH
3
O)
2
C
6
H
3
H 1.3 2.3 nd nd 1.2 10
7
t-6 3,5-(CH
3
O)
2
C
6
H
3
H 1.0 0.9 nd nd <10
6
t-7 4-CH
3
OC
6
H
4
CH
3
3.8 1.7 nd 0 2.8 10
7
c-7 4-CH
3
OC
6
H
4
CH
3
3.5 1.7 nd 0 2.5 10
7
t-8 (4-CH
3
OC
6
H
4
)
2
1.0 0.8 0.2 <10
6
a
Dose, 4.910
4
Gy; [S]=1.0 10
2
M in O
2
-saturated DCE; G value, the yield of oxidation products. Isomerization products were also observed with small G values at
higher conversions in prolonged g-R. nd denotes that the values were note measured.
b
k
O
2
, obtained from the dependence of the decay of S
+
on the concentration of O
2
during pulse radiolysis of S (5.0 10
3
M) in the presence of O
2
in DCE.
c
1-Aryl-2-phenyl-1,2-epoxyethane (aryl=R).
d
Arylmethyl phenyl ketone (aryl=R).
styrene derivatives, 1,1-diphenylethylene, and St at higher concentrations [32,67,7983].
Cycloreversion of r-1,c-2,t-3,t-4- and r-1,t-2,c-3,t-4-tetraphenylcyclobutanes
+
(t,c,t-
TPCB
+
and t,t,t-TPCB
+
, respectively) during g-R in the rigid matrix of glassy BC of
TPCB (5 10
3
M) at 77 K will be described here [42].
Cycloreversion of t,c,t-TPCB
+
Tetraphenylcyclobutane radical cation is expected to decompose into k-type t-St
2
+
, j-type
St
2
+
, or t-St
+
plus t-St. Abroad absorption spectrumof t,c,t-TPCB
+
was detected at 77 K
with weak peaks at 370, 390, 485, 550, and 780 nm, which changed to have clear peaks at
370, 485, 550, and 780 nmupon warming up to 90 K(Fig. 3a). The 48-nmpeak is assigned to
t-St
+
. Photoirradiation of t,c,t-TPCB
+
at 77 K at k over 390 nm gave bands at 400470,
470500, and 680800 nm(Fig. 3b). Warming this sample caused a large increase of the peak
at 350, 550, and 780 nm. The dierence spectrum was obtained by subtracting the spectra
after photoirradiation and warming and indicated the collapse of bands at 400470 and 470
500 nm and the formation of peaks at 350, 550, and 780 nm (Fig. 3c).
Observed spectral changes can be explained by four species: t,c,t-TPCB
+
, t-St
+
, k-
(t-St)
2
+
with peaks at 400470 and 680800 nm [84], and j-St
2
+
with peaks at 350, 550, and
780 nm. Thus t,c,t-TPCB
+
converts to j-St
2
+
upon warming [Eq. (16)], while photo-
irradiation of t,c,t-TPCB
+
at 77 K causes cycloreversion into k-(t-St)
2
+
[Eq. (17)], which
converts to j-St
2
+
upon warming [Eq. (18)]. Finally, j-St
2
+
decomposes into the thermo-
dynamically stable t-St
+
and t-St [Eq. (19)].
t; c; t TPCB
heat ! r St
2
16
t; c; t TPCB
hv ! p t St
2
17
p t St
2
heat ! r St
2
18
r St
2
heat ! t St
t St 19
Cycloreversion of t,t,t-TPCB
+
A broad absorption spectrum of t,t,t-TPCB
+
was observed at 77 K, at 400670 nm with a
peak at 480 nm, and collapsed without any particular spectral change upon warming up to
90 K (Fig. 4). However, the spectrum changed to have clear peaks at 485 and 780 nm upon
photoirradiation at 77 K (Fig. 4a). The absorption spectrum then changed to have a peak
at 550 nm upon warming. The dierence spectrum, obtained by subtracting the spectra
both before and after warming, clearly indicates the collapse of the peak at 485 nm and the
formation of bands at 370, 550, and 770 nm (Fig. 4b).
These results can be interpreted by four species: t,t,t-TPCB
+
, t-St
+
, t-St
+
/t-St
pair with peaks at 485 and 780 nm, and j-St
2
+
. As there was no overlapping of k-electrons
between two benzene rings in the t-St
+
/t-St pair, it is anticipated that the pair has the
same absorption as t-St
+
. Thus t,t,t-TPCB
+
is rather stable up to 90 K and does not
convert to k-(t-St)
2
+
nor j-St
2
+
. Photoirradiation of t,t,t-TPCB
+
at 77 K causes
cycloreversion into t-St
+
/t-St pair [Eq. (20)], which converts to j-St
2
+
upon warming [Eq.
(21)].
t; t; t TPCB
hv ! t St
=t St 20
t St
=t St heat ! j St
2
21
Intermediacy of Stilbene Dimer Radical Cations (St
2
+
)
Cycloreversion of TPCB
+
and dimerization of St
+
are summarized in Scheme 3, in which
k-(t-St)
2
+
, j-St
2
+
, and the t-St
+
/t-St pair are involved as the key intermediates. k-(t-St)
2
+
takes various overlapping arrangements of the k-electrons between two benzene rings, and
exhibits a large charge resonance (CR) band at shorter k of 680800 nm than those of
other dimer
+
reported [84]. On the other hand, j-St
2
+
has an acyclic linear structure,
Figure 3 Absorption spectral changes of t,c,t-TPCB
+
recorded immediately after g-R of t,c,t-
TPCB (5 10
3
M) in glassy BC matrices at 77 K and after warming (a), or after g-R and subsequent
photoirradiation at k longer than 390 nm (1) and after warning (in the order of 2 and 3) (b), and
dierence spectra between spectra after photoirradiation and after warming (DA=A
No. 1
A
No. 2
) (c).
having both a radical and a cation on the 1- and 4-positions of the C
4
linkage. Although
the c-St
2
+
was not detected, the bimolecular reaction of c-St
+
and c-St yields j-St
2
+
or
c-St
+
/c-St pair, which decomposes into thermodynamically stable t-St
+
and t-St.
It should be noted that t,c,t-TPCB
+
decomposes into j-St
2
+
, but t,t,t-TPCB
+
does
not upon warming up to 90 K. On the other hand, photochemical cycloreversion of both
TPCB
+
occurs through cleavage of two CUC bonds to give k-(t-St)
2
+
or t-St
+
/t-St pair.
This may account for the dierent interaction between two phenyl (Ph) groups through the
Figure 4 Absorption spectral changes of t,t,t-TPCB
+
recorded immediately after g-Rof t,t,t-TPCB
(510
3
M) in glassy BC matrices at 77 K and after warming (a), or after g-R and subsequent
photoirradiation at k longer than 390 nm (1) and after warming (in the order of 2 and 3) (b), and
dierence spectra between spectra after photoirradiation and after warming (DA=A
No. 1
A
No. 2
) (c).
CUC bond of cyclobutane ring of t,c,t-TPCB
+
and t,t,t-TPCB
+
in the ground and
excited states.
2.3. Reactions of Radical Cations of Organophosphorus Compounds
Little is known about the reactions of radical cations of organophosphorus compounds
(P
+
) such as aryl phosphates and phosphonates as caged compounds and reagents in
organic syntheses [8591]. To elucidate PET reactions including P
+
as the key inter-
mediate, PR and g-R are used here.
Intramolecular Reaction of Radical Cations of Trinaphthyl Phosphates and Dinaphthyl
Methylphosphonates
From product analysis, uorescence quenching, and LFP, initially formed trinaphthyl
phosphates (9
+
) and dinaphthyl methylphosphonates (10
+
) decompose into 1,1V-
binaphthyl (Np
2
) and 1-naphthyl phosphate or methyl phosphate, respectively. Although
it is suggested that 9
+
and 10
+
change to the intramolecular k-dimer
+
between two Np
Scheme 3 Cycloreversion of TPCB
+
and dimerization of St
+
.
groups and Np
2
+
is subsequently eliminated (Scheme 4), no direct evidence of the
transformation [90,91].
The assignments of 9
+
, 10
+
, and Np
2
+
can be conrmed by their absorption
spectra observed during g-R in BC rigid matrices at 77 K. Three peaks of 9
+
at 400, 680,
and 720 nm and two broad bands in the region of 500600 and 800850 nm were observed
after the g-R of 9 in BC rigid matrix at 77 K (Fig. 5). The absorption spectrum
Scheme 4 Elimination of Np
2
+
from 9
+
through the intramolecular k-dimer
+
.
Figure 5 Absorption spectral changes of 9
+
and 10
+
recorded immediately after g-R of 9 at 3
10
2
M (a) and 10 at 1 10
2
M (b) in BC rigid matrices at 77 K and after warming. Arrows show
decrease in the peak upon warming.
disappeared with no formation of a peak upon warming with independence on [9]. The
broad band in the region of 500600 nm, assigned to an intramolecular k-dimer
+
of 9
+
with face-to-face interaction between the two Np groups, disappeared faster than the
peaks of 9
+
at 400, 680, and 720 nm (Fig. 5a). Similar spectral changes of 10
+
were
observed during g-R of 10 in BC rigid matrix at 77 K (Fig. 5b).
The transient absorption spectrum assigned to 9
+
and intramolecular k-dimer
+
of
9
+
was observed immediately after 8-nsec e
, and decayed with the formation of newpeaks

at 480 and 520 nmassigned to Np
2
+
(Fig. 6). This indicates that intramolecular dimerization
in 9
+
occurs to reversibly form k-dimer
+
at k
d
intra
= 1.0 10
8
1.0 10
9
sec
1
. In DCE,
9
+
and k-dimer
+
disappeared by neutralization with Cl
generated by the initial radiolytic

processes at k
n
= 4.7 10
10
M
1
sec
1
. From the time prole of the transient absorption
at 520 nm involving the formation of Np
2
+
and decay of k-dimer
+
of 9
+
, k
r
= 5.3
10
5
sec
1
is estimated for the reaction.
Warming up to 90 K is not enough for the activation barrier for the formation of
Np
2
+
fromk-dimer
+
of 9
+
, while the reaction is completely attained even for e
duration
of 8 nsec at r.t. The peaks of k-dimer
+
of 9
+
were much broader than that of k-dimer
+
of
1,3-di-1-naphthylpropane
+
(720 nm) because of the dierent spacers, OUP(O)UO and
(CH
2
)
3
, between the two Np groups in 9
+
and 1,3-di-1-naphthylpropane
+
, respectively.
No elimination of Np
2
+
occurs in 1,3-di-1-naphthylpropane
+
and bis(1-naphthyloxy)
methane
+
. The electron withdrawing character of the P(O) group in the OUP(O)UO
spacer may be responsible for the elimination of Np
2
+
.
Figure 6 Transient absorption spectra of 9
+
observed immediately (open circle), 5 Asec (solid
triangle), and 20 Asec after e
(gray square) during PR of 1.010

2
M of 9 in DCE at r.t.
Attachments are time proles of DO.D.
400
and DO.D.
520
.
Bimolecular Reaction of p-Substituted Triphenylphosphines Radical Cation with Water
From the product analyses of PET reactions of trivalent phosphorus compounds such as
phosphines and phosphates, it is found that P
+
reacts with nucleophiles such as water and
alcohol to yield phosphine oxides and phosphates [9295]. During a reaction of triphenyl-
phosphines (P(C
6
H
4
-X-p)
3
+
) with water to give phosphine oxides OjP(C
6
H
4
-X-p)
3
(Scheme 5), electron-donating character of the p-substituent shifted the bands of P(C
6
H
4
-
X-p)
3
+
to longer k (520610 nm) and decreased the yield of OjP(C
6
H
4
-X-p)
3
(0.260.02)
on the basis of LFP, PR, g-R, and product analysis [96].
The positive charge on the P atom of P(C
6
H
4
OMe-p)
3
+
is less than P(C
6
H
5
)
3
+
be-
cause of conjugation with the k-electrons of the benzene ring and the n-electrons of O atom
of p-MeO. Thus, the k
r
of P(C
6
H
4
OMe-p)
3
+
with H
2
O is smaller than that of P(C
6
H
5
)
3
+
.
The delocalization of the positive charge of 3
+
may be related to the longer k shift of the
bands with an increase in the electron-donating character of p-substituent. The dierence of
reactivities of P(C
6
H
4
-X-p)
3
+
fromthose of 9
+
and 10
+
is a consequence of the respective
HOMO, which are the phosphorus nonbonding orbital and Np k-orbital, respectively.
3. DIMERIZATION OF RADICAL ANIONS
Whether or not the radical anion of aromatic hydrocarbons (ArH
) is stabilized by CR k-
interaction with ArH, giving the dimer radical anion, (ArH)
2
, is an interesting subject.
Although much eort has been concentrated on detecting (ArH)
2
with a sandwich
structure between two aromatic groups of ArH
(and ArH, the formation of (ArH)

2
(has
not been observed [46,47,73,97111]. As an exceptional case, (anthracene)
2
has been
formed from the cleavage of a 4k+4k anthracene photodimer
in a rigid matrix at 77 K
[102]. Radical anions of several olens with electron-withdrawing substituents such as
fumaronitrile, maleic anhydride, and acrylonitrile have been observed to dimerize to give
the dimer
which are assumed to have a broad CR band in the 8002000 nm range [101].
In contrast to St
+
forming k- and/or j-(St)
2
+
, no dimerization of St
with St has been

observed. It has been reported that St
reacts with St
to give the stilbene dianion (St

2
)
and St via disproportionation [106,107] at higher concentrations of St
.
3.1. Dimer Radical Anions of Aromatic Acetylenes [48]
Diphenylacetylene
(11a
) reacts with 11a
to give the 11a dimer dianion, (11a)

2
2
with
a peak at 470 nm (e
470
=9.0 10
3
and 1.1 10
4
M
1
cm
1
in THF [107] and HMPA [108],
Scheme 5 Reaction of P(C
6
H
4
-X-p)
3
+
with water to give OjP(C
6
H
4
-X-p)
3
.
respectively) at higher [11a
]=(2.67.3) 10
2
and 3.5 10
3
M in THF[107] and
HMPA [108], respectively. The structure of (11a)
2
2
is assumed to be the 1,2,3,4-
tetraphenylbut-1,3-ene-1,4-diyl dianion (PhC
= CPhUCPh = C
Ph) with the formation

of one CUC bond between two sp carbons [107,108]. On the other hand, it was found that
aromatic acetylene
(A
) (Scheme 6) such as 11a
11g
and 1,4-diphenyl-1,3-
butadiyne
(12
) dimerizes with A to form A

2
. The intramolecular dimerization occurs

in 1,N-di-(4-(diphenylacetylenyl))-ethane
(13
(n = 2)), -propane
(13
(n = 3)), -
butane
(13
(n = 4)), -pentane
(13
(n = 5)), and -hexane
(13
(n = 6)) to give
the intramolecular dimer
between two 11a-chromophores during g-R in MTHF rigid

matrices at 77 K and PR in HMPA and DMF solutions at r.t.
Formation of Intermolecular Dimer Radical Anions
Transient absorption spectrum with peaks at 450 and >840 nm assigned to 11a
was
observed immediately after e
during PR of 11a at 5.0 10

3
4.0 10
2
M in HMPA at
r.t. (Fig. 7) and g-R in an MTHF rigid matrix at 77 K (Fig. 8) [73], and during the
reduction by Na in THF and HMPA [107,108]. The transient absorption of 11a
decayed
on a time scale of a few Asec with formation of a band at 500 nm with isosbestic points at
470 and 630 nm at r.t. The pseudo-rst-order rate constants of the decay of 450-nm band
and formation of 500-nm band were calculated to be k
d
450
=1.0 10
6
and k
f
500
=1.3 10
6
sec
1
, respectively, at [11a]=10
2
M. It is found that k
decay
450
and k
form
500
increase with
increasing [11a]. This suggests that 11a
dimerizes with 11a to give (11a)

2
with the
formation of 500-nm band. A similar absorption spectral change of 11a
was observed in
the MTHF rigid matrix at 77 K during g-R of 11a (Fig. 8). Formation of (11a)
2
is
completely contrary to previous results of electrolysis, the reduction by Na, photolysis,
and radiolysis of 11a where no dimerization was observed. k
d
=(3.86.6) 10
7
M
1
sec
1
for the dimerization was calculated from the linear plots of k
decay
450
and k
form
500
vs. [11a].
j-Type or diene-type stucture is most likely for (11a)
2
with 500-nm band (Scheme 7),

because (11a)
2
2
, PhC
jCPhCPhjC
Ph, has similar band at 470 nm [107,108].

Scheme 6 Aromatic acetylene
(11a
11g
, 12
, and 13
(n=26)).
k
d
for dimerization of other 11
and 12
were determined (Table 6). k

d
=(4.16.6)
10
7
M
1
sec
1
for 11a
11c
with weak electronic substituents such as 4-Me and 4-Ph is

larger than k
d
= 7.3 10
6
1.7 10
7
M
1
sec
1
for 11d
11g
with strong electronic

substituents such as 4-nitro, 4-MeO, 4-uoro, and 2,3,4,5,6-pentamethyl groups. The
dimerization of 11
and 11 is inhibited by steric and electronic eects of the substituents

causing a higher barrier to a CUC bond formation between two sp carbons.
Figure 8 Absorption spectral changes of 11a
upon warming up to 90 K after g-R of 11a at

5.010
3
M in MTHF rigid matrix at 77 K.
Figure 7 Transient absorption spectral changes of 11a
during PR of 11a at 1.0 10

2
M in
HMPA at r.t. Insets: time proles of DO.D.
450
and DO.D.
500
.
Almost equivalent results were observed during PR and g-R of 12. Therefore, 12
dimerizes with 12 to 12
2
with a peak at 560 nm (Scheme 8). k

d
for 12
is almost
equivalent with that for 11a
.
Formation of Intramolecular Dimer Radical Anions
The formation of intramolecular dimer
, j-(11a)
2
between 11a
and 11a was found to

occur in 13
(n = 26) having two 11a-chromophores linked by a di-to-hexa methylene

(Scheme 9). k
d
intra
= (3.46.3) 10
5
sec
1
for the intramolecular dimerization was almost
constant for 13
(n =26). The intermolecular dimerization of 13
and 13 at [13] =1.0

10
3
to 2.5 10
2
M was not observed on a time scale of a few Asec. This seems to be
attributed to the 4-C
6
H
4
CCPh substituent of 13
and 13 at the 4-position because of the

electronic and steric eects.
The DO.D.
510
of j-(11a)
2
in 13
(n=2, 3, 5, and 6) was much smaller in comparison,

while that of j-(11a)
2
in 13
(n = 4) was comparable to that of intermolecular j-(11a)

2
.
The yield of j-(11a)
2
in 13
(n=4) was signicantly high among 13
(n = 26) and
comparable with that of intermolecular (11a)
2
. Although the n=3 rule is eective for the

intramolecular k-interaction of ArU(CH
2
)
n
UAr in the excited state [112], n=4 is eective
for that of intramolecular j-(11a)
2
in 13
.
No direct evidence for the formation of k-A
2
suggests that A
is stabilized by the
formation of j-A
2
with a CUC bond between two sp carbons of A
and A and that the

formation of j-A
2
is responsible for the CUC triple bonds of A
and A.
3.2. Intramolecular Dimer Radical Anions in Diarylmethanols
The formation of an intramolecular dimer
of diaryllmethanol (Ar
2
CHOH, 14ae) was
found as the intermediates in the attachment of e
s
(Scheme 10) during PR and g-R in

DMF and 77 K MTHF matrix, respectively [113].
Transient absorption spectrum showed a peak at 330 nm assigned to diphenylmethyl
radical Ph
2
CH
immediately after e
(8 nsec) during PR of 14a (5.0 10

3
M) in DMF.
Transient absorption of 14a
was not observed. On the other hand, the transient

absorption spectrum with a peak at 328 nm assigned to 14b
was observed immediately

after e
, and decayed with formation of peaks at 362 and 530 nm assigned to Ar

2
CH
and a
byproduct from 14b
, respectively, during PR of 14b (Fig. 9). This indicates that

introduction of electron-withdrawing groups such as CN and CO
2
CH
3
on the benzene ring
retarded the CUO bond dissociation of 14
. 14be
decayed slowly to give the

corresponding Ar
2
CH
obeying a rst-order kinetics (k

r
= (23) 10
5
sec
1
) and s of
14
was independent of the mono- or disubstitution.

Scheme 7 j-Type or diene-type dimer
(11a)
2
from dimerization of 11a
and 11a.
Table 6 Intermolecular Dimerizations of A
and A (A=11 and 12)

a
k
max
[nm] DO.D.
max
A
Substituents A
A
2
A
2
[A
2
]
max
/[A
]
0
e
max
[M
1
sec
1
] of A
k
d
[M
1
sec
1
] Solvent
11a
4-H 450 500 1.8 1.0 0.56 5.4 10

4
6.6 10
7
HMPA
11b
4-CH
3
450 510 1.4 0.9 0.66 4.1 10
4
5.7 10
7
HMPA
11c
4-C
6
H
5
500 550 1.6 1.2 0.77 4.7 10
4
4.1 10
7
HMPA
11d
4-NO
2
440 490 0.95 0.09 0.10 2.7 10
4
9.0 10
6
HMPA
11e
4-OCH
3
440 500 1.7 0.15 0.09 5.2 10
4
1.0 10
7
HMPA
11f
4-F 440 500 1.8 0.25 0.15 5.4 10

4
1.7 10
7
HMPA
11g
(CH
3
)
5
450 540 3.9 0.25 0.06 1.2 10
5
7.3 10
6
HMPA
11a
4-H 450 510 0.61 0.05 0.09 5.4 10

4
8.0 10
6
DMF
12
H 480 560 1.0 0.10 0.10 8.9 10

4
8.2 10
6
DMF
a
[A
2
]
max
/[A
]
0
=(DO.D.
max
at k
max
for A
2
)/(DO.D.
0
at k
max
for A
). e
max
was calculated from DO.D.
0
at k
max
for A
, e
max
=5.4 10
4
M
1
cm
1
for 11a
, l=0.4 cm,
and [11
]0=8.3 10
5
M in HMPA, while e
480
for 12
was calculated from e

450
=5.4 10
4
M
1
cm
1
for 11a
, l=0.4 cm, and [11a
]
0
=2.8 10
5
M in DMF. k
d
for
the dimerization of A
and A was calculated from the linear plot of k

f
for the formation A
2
vs. [A].
Scheme 9 Intramolecular dimerization of 11a
and 11a in 13
.
Scheme 8 j-Type or diene-type dimer
12
2
from dimerization of 12
and 12.
Scheme 10 Intramolecular dimer
during electron attachment of 14ae.

The time-resolved absorption spectra of e
s
in DMF and 14b
in the range
of 8001600 nm were obtained from the decay curve measured at every 100-nm step
(Fig. 10). While the peak of e
s
was at 1400 nm, that of 14b
was at >1600 nm. Although

the NIR absorption spectra peaked at 1780 and 1930 nm were observed during the g-R of
14b and 14c (5 10
3
M), respectively, in MTHF at 77 K, no peak was observed in this
region for 14d,e (Fig. 11). From the structureless feature of the spectra similar to those
reported for CR band of dimer
[101,102,114,115], we assigned them to the CR band of

the intramolecular dimer
of 14b,c
. From the peak k, CR energies (DH

CR
) were
determined to be 8.0 and 7.4 kcal mol
1
for 14b
and 14c
, respectively. The absence of

CR band for mono-substituted alcohols 14d,e
also supported the assignment of the

intramolecular dimer
of 14b,c
.
Although an intramolecular singlet excimer (
1
Ar
2
*
) uorescence of 1,3-bis(4-cyano-
phenyl)propan-1-ol was observed in MTHF at r.t., no CR band of 1,3-bis(4-cyanophenyl)-
propan-1-ol
was observed during PR and g-R. An unsymmetrical structure of 1,3-bis

(4-cyanophenyl)propan-1-ol does not inhibit
1
Ar
2
*
formation [112]. Although two Np-chro-
mophores have been suggested to form intramolecular Np
2
in 1,3-di-h-naphthylpro-
panes
, no CR band of 1,3-di-a-naphthylpropane
and 1,3-di-1-pyrenyl-propane
was
Figure 9 Transient absorption spectra of 14
observed during PR of the DMF solutions of 14a

(a) and 14b (b).
observed during g-R in 77 K MTHF matrix. The PR of 1,3-di-1-pyrenylpropane in THF
and 1,3-di-h-naphthylpropan-1-ol in DMF at r.t. showed transient absorptions of pyrene
and Np
, respectively, without the CR band of Ar

2
, although PR of these compounds in

DCE gave the corresponding Ar
2
+
of pyrene
+
and Np
+
. Ar
2
of methylterephthalate-
chromophore was assumed from the kinetic study on the anion radical transfer from
methylterephthalate to 1,4-dicyanobenzene in diester of 1,n-alkanediols [116]. These suggest
that Ar
2
formation may dier from the n =3 rule for

1
Ar
2
*
formation, probably due to the
repulsion energy higher than DH
CR
[112]. The 1,1-diarylmethyl structure is considered to be
Figure 11 NIR absorption spectra of 14ae
during g-R of 14ae in MTHF at 77 K. The spectra

were subtracted by those before photoirradiation.
Figure 10 Transient absorption spectral change of 14b
in the NIR region (CR band) obtained

from decay curves during PR of 14b in DMF.
eective for Ar
2
formation being dierent from

1
Ar
2
*
as suggested for intramolecular
3
Np
2
*
[117]. While the sandwich-pair is preferred for
1
Ar
2
*
, the L-shaped conformation as in the
most symmetric conformation of 1,1-di-a-naphthylmethane and cis-6b,12b-dihydroace-
naphth(1,2-a)acenaphthylene (the Agosta dimer) could be favored for
3
Np
2
*
[117] and the
1,1-diarylmethyl structure would be preferred for intramolecular Ar
2
of 1b,c
rather than
displaced sandwich-pair structure favored for Ar
2
+
.
4. LIFETIMES OF RADICAL CATIONS AND ANIONS IN THE
EXCITED STATE
Excitation of M
+/
increases its electron acceptor and donor characteristics, respectively,

because an electron is promoted from a low-energy MO to a higher-energy MO [1,5].
Electron transfer (ET) reactions catalyzed by M
+
*
/
* have been studied at electrode

surfaces [20,118] and in solution [23,25,26,33,119]. M
+
*
/
* is usually nonluminescent in
solution, although weak luminescences of thermally stable M
+/
such as the anthra-

quinone
and N-methylphenothiazine
+
have been reported at 470580 nm [120,121] and
at 600 nm [25], respectively. Breslin and Fox [33] have reported the weak luminescence of
two substituted triarylamine
+
with luminescence peaks at 790 and 803 nm and with u
f
=
10
5
, while the other thermally stable M
+/
investigated was nonluminescent. They have

concluded that the internal conversion from the lowest excited doublet state (D
1
) to the
ground doublet state (D
0
) proceeds as the primary deactivation pathway for M
+/
(D
1
)
because of the small energy between D
1
and D
0
states.
4.1. Lifetime of Stilbene Radical Cation in the Excited State (St
+
*) by the
Hole Transfer Quenching
It is assumed that the photochemical c!t one-way isomerization of c-St
+
to t-St
+
occurs
in rigid matrices at 77 K [40,122] and in solution at r.t. on the basis of LPF of c-St
+
formed by using PR in DCE [83] or secondary ET in acetonitrile [32]. The photochemical
c!t isomerization has been reported to take place in the second excited doublet state (D
2
)
but not in c-St
+
(D
1
) [83]. Because St
+
(D
2
) is nonluminescent, H of St
+
(D
2
) must be
determined by using other experiments such as the excitation energy (E
ex
) quenching or
hole transfer (HT) quenching. Because St
+
(D
2
) has a higher E
ox
than St
+
(D
0
) [1,5], HT
occurs from St
+
(D
2
) to an appropriate quencher (Q). H of St
+
(D
2
), as well as the 1,2-
diphenylcyclo-1-butene
+
(DPCB
+
), as a structurally constrained derivative of c-St, was
estimated from selective HT quenching of St
+
(D
2
) using anisole (AN) as Q through the
PR-LFP combined method [43,83,123125].
Lifetime of t-St
+
*
It is well established that c-St
+
and t-St
+
are selectively generated during the PR of c-St
and t-St in DCEat r.t., and they showbands at 420580 and 700850 nmassigned to D
2
pD
0
and D
1
pD
0
transitions, respectively, and peaks at 515 and 780 nm for c-St
+
and 480 and
760 nm for t-St
+
[42,73,83]. Excitation of St
+
with hv
532
generates St
+
(D
2
) (St
+
*) with
E
ex
=50 and 53 kcal mol
1
for c-St
+
* and t-St
+
*, respectively, that were calculated from
the red edges of bands at 420580 nm.
Irradiation of t-St
+
with hv
532
exhibited no change in the transient absorption
spectra and time proles of DO.D.
480
, where t-St
+
shows a peak (Fig. 12a). Therefore t-
St
+
* does not isomerize to c-St
+
(D
0
) with photoirradiation, but decays to t-St
+
(D
0
)
through internal conversion at k
ic
t
(Scheme 11).
The photoirradiation of t-St
+
in the presence of AN caused a decrease of DO.D.
480
immediately after hv
532
(Fig. 12b). jDO.D.
480
j increased with increasing [AN]. It is obvious
that t-St
+
* is quenched by AN via HT quenching to give t-St and AN
+
with the
bimolecular HT rate constant of k
ht
(Scheme 11). The recovery of DO.D.
480
after hv
532
corresponds to HT fromAN
+
to t-St to yield AN and t-St
+
[73], which occured at k
di
=
7.8 10
9
M
1
sec
1
. The k
ht
= k
di
can be assumed because of the large exothermicity of
Figure 12 Kinetic traces illustrating time proles of DO.D.
480
as a function of time during PR
LFP experiment of t-St (5 10
3
M) in the absence (a) and presence (b) of AN (1 M) in DCE.
Scheme 11 Hole transfer quenching of t-St
+
* by AN.
DG = 25 kcal mol
1
for HT from St
+
* to AN. From the linear SternVolmer plots of
Y
t
1
vs. [AN]
1
, where Y
t
is the chemical yield of [t-St
+
]
disapp
, s
t
, and k
ic
t
for t-St
+
(D
2
)
were calculated to be 240F50 psec and (4.1F1.1) 10
9
sec
1
, respectively.
Lifetime of c-St
+
* and DPCB
+
* (DPCB=1,2-diphenylcylclobutene)
In contrast to t-St
+
*, c!t one-way isomerization of c-St
+
* to t-St
+
was observed
within hv
532
(5 nsec) [32,83]. From the transient spectral changes and time proles of
DO.D.
515
and DO.D.
480
of c-St
+
and t-St
+
, respectively (Fig. 13), the photochemical
conversion of c-St
+
per hv
532
is (80 F 15)% at [c-St
+
]
0
= 1.5 10
5
M before photo-
irradiation, and the chemical yield of t-St
+
from c-St
+
(D
2
) is (75 F 15)%. The remain-
ing (25F15)% of c-St
+
that disappeared is considered to convert to c-St, t-St, or a radical
cation as a product such as dihydrophenanthrene.
The u of photochemical c!t isomerization of c-St
+
to t-St
+
was subsequently
determined to be 0.65F0.15 from c-St
+
that disappeared (u
c
) and 0.49F0.12 from t-St
+
that formed (u
t
). Taking into account u
c
and u
t
, as well as the conversion of (80 F15)%for
c-St
+
per hv
532
, c-St
+
* isomerizes to t-St
+
at (49 F 12)%, converts to other products at
(16F4)%, and deactivates to c-St
+
at (35 F 8)% yield.
The transient phenomena of c-St
+
* that involved the isomerization and HT
quenching of c-St
+
* using AN are shown in Scheme 12. According to Scheme 12, the
linear SternVolmer plots of s
t
/s
t
AN
vs. [AN] aorded s
c
= 120 F 30 psec being one-half
of s
t
at k
ht
= k
di
= 7.8 10
9
M
1
sec
1
. k
i
, k
p
, and k
ic
c
were determined to be (4.1 F 1.0)
10
9
, (1.3 F 0.3) 10
9
, and (2.9 F 0.7) 10
9
sec
1
, respectively.
Because 1,2-diphenylcyclo-1-butene (DPCB) has a rigid planar structure with the c-
St-chromophore structurally constrained by the cyclobutene ring, and because it is stable
for geometrical isomerizations, TPCB
+
is expected to have the same rigid planar
structure. Pulse radiolysis of DPCB in DCE produces DPCB
+
, which shows bands at
Figure 13 Transient absorption spectra recorded before hv
532
(o) and immediately after (.) and
200 nsec (D) and 1 As (E) after hv
532
during PRLFP of c-St (510
3
M) in DCE (a). Kinetic traces
illustrating time proles of DO.D.
480
(b) and DO.D.
515
(c) as a function of time after e
.
420560 and 700850 nm that are assigned to D
2
pD
0
and D
1
pD
0
transitions, respec-
tively [42,73,83]. Excitation of DPCB
+
at 532 nm exhibited no change in the transient
absorption. Therefore, DPCB
+
* is deactivated to DPCB
+
(D
0
) within hv
532
, similarly to
t-St
+
* (Scheme 11). Photoirradiation of DPCB
+
in the presence of p-methylanisole
(MA) caused a decrease of DO.D.
480
immediately after hv
532
with an increasing [MA]. It is
obvious that DPCB
+
* is quenched by MA via HT quenching to give DPCB and MA
+
.
From the linear SternVolmer plots of Y
CB
1
vs. [MA]
1
, s
DPCB
and k
ic
DPCB
of DPCB
+
* were calculated to be 380 F 30 psec and (2.6 F 0.2) 10
9
sec
1
, respectively, at k
ht
=
k
di
= 7.8 10
9
M
1
sec
1
. Consequently, it is concluded that H
DPCB
is longer than s
c
and
s
t
, whereas k
ic
DPCB
is comparable with k
ic
c
and k
ic
t
(Table 7).
Comparison of c-St
+
*, t-St
+
*, and DPCB
+
*
Similar to most M
+
*, c-St
+
*, t-St
+
*, and CB
+
* are nonluminescent. Isomerization of
c-St
+
* to t-St
+
, which proceeds via twisting about the central CjC double bond as a
main process, competes with the internal conversion of c-St
+
*. However, t-St
+
* and
DPCB
+
* are deactivated to the D
0
state without any other reactions. Although t-St
+
*
could slightly twist, it does not isomerize to c-St
+
. The twisting is faster in c-St
+
* than in
t-St
+
* because of the interactions between the Ph groups of c-St. Because the twisting is
severely hindered by structural constraints in DPCB, DPCB is unable to change its initial
planar rigid structure. Both DPCB
+
* and DPCB
+
(D
0
) probably have the rigid planar
structure. The energy levels of c-St
+
*, t-St
+
*, and DPCB
+
* are assumed to be almost
equivalent because of the similar E
p/2
ox
for c-St, t-St, and DPCB, as well as the similar E
ex
of c-St
+
*, t-St
+
*, and DPCB
+
* (Table 7). It is suggested that c-St
+
*, t-St
+
*, and
DPCB
+
* exist in potential minima, and that the order s
c
<s
t
<s
DPCB
is mainly attributed
Table 7 Properties of t-St
+
, c-St
+
, and DPCB
+
in the D
2
State: Lifetime (s), Rate Constants
for Internal Conversion (k
ic
), ct Isomerization (k
i
), and Product Formation (k
p
), and Excitation
Energy (E
ex
)
Radical Cations in D
2
t-St
+
* c-St
+
* CB
+
*
s[psec] 240F50 120 F 30 380 F 30
k
ic
[sec
1
] (4.1 F 1.1) 10
9
(2.9 F 0.7) 10
9
(2.6 F 0.2) 10
9
k
i
[sec
1
] 0 (4.1 F 1.0) 10
9
0
k
p
[sec
1
] 0 (1.3 F 0.3) 10
9
0
E
ex
[kcal mol
1
] 53 50 51
Scheme 12 Reactions of c-St
+
* involving isomerization, ic, and HT quenching.
to the isomerization via twisting only in c-St
+
*. It is clear that the twisting is favorable in
c-St
+
*, slightly favorable in t-St
+
*, but not at all in DPCB
+
*.
Considering u
f
, s, and ct isomerization for St*, it is clearly suggested that the
transient phenomena of St
+
(D
2
) cannot be assumed on the basis of those for St(S
1
).
Judging from s
c
f
120 psec and H
t
f
240 psec, a diabatic process is proposed for the
isomerization of c-St
+
* to t-St
+
. It has been proposed the analogous process in which c-
St
+
* avoidably crosses with c-St
+
(D
1
), followed by an allowed crossing to t-St
+
(D
0
)
at the 40j twisted geometry against a planar c-St
+
*, where the D
2
, D
1
, and D
0
states
closely lie, on the basis of MO calculations [32]. The barrier for the twisting of c-St
+
* is
estimated to be 0.32 kcal mol
1
, if k
i
values are assumed to be 5.3 10
9
sec
1
for the
largest limit and 2.9 10
9
sec
1
for the smallest limit at 300 and 140 K, respectively, on
the basis of the error limits (F30%) for u and k
i
. This suggests that c-St
+
* is stabilized by
twisting at a shallow potential minimum, and that conversion to another product can
compete with isomerization. Consequently, the diabatic isomerization from c-St
+
* to t-
St
+
is strongly expected to take place via an avoidable crossing from c-St
+
(D
2
) to c-St
+
(D
1
), and then to t-St
+
(D
0
) with a small barrier.
In conclusion, selective HT quenching of St
+
* and CB
+
* by AN and MA yielded
s
c
=120, s
t
=240, and s
DPCB
=380 psec, which is attributed to the isomerization via the
twisting only in c-St
+
*. It is also suggested that diabatic isomerization from c-St
+
* to t-
St
+
proceeds via an avoidable crossing of the D
2
, D
1
, and D
0
states. To determine the s of
M
+
* with k
ht
=k
di
can be essentially applied to any M
+
*, although it is necessary to
nd an appropriate molecule as a selective hole quencher. Moreover, the s of M
+
* must
be longer than 50 psec, because [AN] is 2 M at the maximum to keep the solvent property.
4.2. Lifetime of St
**
by the Electron Transfer Quenching
Characterizations of St
(D
2
) are necessary to elucidate the isomerization of St
(D
2
),
which is nonluminescent, similarly to radical anions of aromatic compounds in the excited
states [25,33,118,120,121,126130]. Selective electron transfer (ET) quenching of St
(D
2
)
was performed using biphenyl (Bp) as an electron acceptor and H of St
(D
2
) was
estimated using a PRLFP combined method [43,46,83,123125,131,132].
It is well established that c-St
and t-St
are selectively generated during PR of c-St

and t-St in DMF at r.t., and these show bands at 420580 and 700850 nm which are
assigned to D
2
pD
0
and D
1
pD
0
transitions, respectively, and peaks at 515 and 780 nm for
c-St
and 500 and 760 nm for t-St
[42,49,83,133]. Excitation of St
with hv
532
generates
St
(D
2
) (St
*) with E
ex
=45 and 48 kcal mol
1
for c-St
* and t-St
*, respectively.
Irradiation of t-St
with hv
532
caused a decrease of DO.D. immediately after hv
532
, while
no spectral shift was observed.
Photoelectron Ejection from t-St
* and Electron Transfer Quenching of St
*
The dierences in DO.D. before and after hv
532
(jDO.D.j) decreased with increasing [t-St].
The spectrum of t-St
was recovered on a time scale of 1030 nsec after hv

532
, depending
on [t-St]. These results show that photoelectron ejection from t-St
occurs and that the

electron is captured by t-St. It is also indicated that t-St
* does not isomerize to c-St
(D
0
), but decays to t-St
(D
0
) with k
ic
t
of t-St
*. u
e
t
= 0.06 F 0.02 of photoelectron
ejection from t-St
was measured.
The ET quenching of c-St
(D
2
) and t-St
(D
2
) (c-St
* and t-St
*) by an ET
quencher Bp was examined. Transient absorption spectra composed of bands of St
and
Bp
with peaks at 405 and 630 nm at the ratio of [Bp]/[St] = 2100 were observed
immediately after e
during PRof mixture of St and Bp with [St] =5 10

3
Mand [Bp] =1
10
2
5 10
1
M(Fig. 14). The transient absorption spectrumchanged to that of St
on
the time scale of 50200 nsec after e
depending on [St], because the exergonic ETfromBp
to St (DG=11 kcal mol

1
) proceeds stoichiometrically at k
di
[134,135]. When t-St
was
irradiated with hv
532
, DO.D.
500
decreased immediately after hv
532
, and DO.D.
405
increased
with an increase of [Bp] (Fig. 15). This indicates that t-St
* is quenched by Bp via ETto give

t-St and Bp
within hv
532
. The decay in DO.D.
405
and recovery of DO.D.
500
after hv
532
correspond to ET from Bp
to t-St to yield Bp and t-St
at k
et
= k
di
.
Electronic transfer quenching of t-St
* proceeds at k
et
= k
di
= 7.1 10
9
M
1
sec
1
in DMF. Similar to radical ion pair, (D
+
/A
)
solv
formed during ET between donor
(D) and acceptor (A) molecules in the excited singlet or triplet state, it is suggested that ET
quenching initially gives (St/Bp
)
solv
with competition of the internal conversion of St
*
to St
. (St/Bp
)
solv
then undergoes solvent separation into St and Bp
at k
sep
or returns
to St
and Bp via back ET at k

et
. Therefore, the fraction of free Bp
formed is
represented by R=k
sep
/(k
et
+k
sep
).
Transient Phenomena of t-St
* and c-St
*
Photoelectron ejection from ArH
in nonpolar solvents has been interpreted in terms of

autoionizing excited states with s = 10
14
sec, which can also be internally converted to the
D
0
states [34,35,136,137]. It is assumed that t-St
* in the vibrational excited state ((t-St
*)
z
)
undergoes vibrational relaxation on the time scale of 10
14
sec to yield t-St
*, which has a
long enough lifetime H
t*
= (k
d
t
)
1
to be quenched by Bp via ET involving (t-St/Bp
)
solv
(Scheme 13). u
e
t
=0.06 F0.02 suggests that (t-St
*)
z
undergoes photoelectron ejection and
vibrational relaxation to t-St
* in 6% and 94% yields, respectively. The experimental

results show that 014%of t-St
* is quenched by Bp depending on [Bp], while the rest of t-

St
* undergoes internal conversion to the D

0
state. Fromthe linear plots of (B
t
Bp
u
e
l
)
1
or
Figure 14 Transient absorption spectra recorded immediately after e
(o), and before (.) and

immediately after (D) hv
532
during PRLFP of a mixture of t-St (5 10
3
M) and Bp (1 10
1
M) in
DMF. The delay time of hv
532
from e
was 75 nsec.
Figure 15 Kinetic traces illustrating the time proles of DO.D.
405
and DO.D.
500
as a function of
time after e
during PRLFP of mixtures of t-St and Bp. [t-St]=5 10

3
, [Bp]=0 (a), 2 10
2
(b),
5 10
2
(c), 1 10
1
(d), and 5 10
1
M (e). The delay time of hv
532
from e
was 75 nsec.
Scheme 13 Electron transfer quenching of t-St
* by Bp.
u
Bp
1
vs. [Bp]
1
, s
t
and k
ic
t
were estimated to be 2.5 F 0.7 nsec and (4.0 F 1.2) 10
8
sec
1
,
respectively. Because R=k
sep
/(k
et
+k
sep
) =0.15 F0.4 is calculated fromthe intercept and
u
t
= 0.94, the back ET with DG = 11 kcal mol
1
occurs six times faster than the solvent
separation within (t-St/Bp
)
solv
.
Isomerization of c-St
* to t-St
was observed within hv

532
. The time proles of
DO.D.
520
and DO.D.
500
assigned to c-St
and t-St
, respectively (Fig. 16), demonstrated

that the photochemical conversion of c-St
per hv
532
is 49% and that the chemical yield of
[t-St
]
form
from [c-St
]
cons
is 67%. The remaining 33% of c-St
consumed is considered
to give c-St via photoelectron ejection. The us of [c-St
]
cons
and [t-St
]
form
were
measured to be u
c
= 0.21 F 0.05 and u
t
= 0.14 F 0.03, respectively. Photoelectron
ejection of (c-St
*)
z
occurs competitively with vibrational relaxation to c-St
*, and
therefore, u
e
c
was calculated from u
e
c
= u
c
B
t
to be 0.07 F 0.02, which is similar to that
for (t-St
*)
z
, u
e
t
=0.06 F 0.02. Summarizing, (c-St
*)
z
undergoes photoelectron ejection
and vibrational relaxation to c-St
* in 7% and 93% yields, and the isomerization and

internal conversion of c-St
* occur in 15% and 85% yields, respectively.

After the exergonic ET from Bp
to c-St yielding Bp and c-St
stoichiometrically
at k
di
, c-St
was irradiated with hv

532
during the PRLFP of mixture of c-St and Bp
(Fig. 17). DO.D.
520
decreased and DO.D.
405
increased immediately after hv
532
, while
DO.D.
500
increased on the time scale of 10100 nsec depending on [Bp] (Fig. 18). Based
Figure 16 Transient absorption spectra recorded before hv
532
(o) and immediately (.) and 1.4
Asec (D) after hv
532
during PRLFP of c-St (5 10
3
M) in DMF (a). Kinetic traces illustrating time
proles of DO.D.
500
and DO.D.
520
as a function of time after e
(b). The delay time of hv

532
from e
was 70 nsec.
on Scheme 14, the linear plot of u
Bp
1
vs. [Bp]
1
was obtained. s
c
was calculated to be
1.5F0.4 nsec and found to be shorter than s
t
, fromk
et
s
c
, assuming k
et
=k
di
. On the basis of
k
i
:k
ic
c
= 1:5.7 and s
c
, k
i
and k
ic
c
were calculated to be (1.0 F0.3) 10
8
and (5.6 F1.7) 10
8
sec
1
, respectively. R=k
sep
/(k
et
+k
sep
) =0.18 F0.4 is almost equal to Rfor (t-St/Bp
)
solv
because of the nearly equivalent DG = 11 kcal mol
1
for the back ET in (St/Bp
)
solv
.
Comparisons Between St
* and St
+
*
Isomerization of c-St
* to t-St
competes with the internal conversion of c-St
*, while
only internal conversion occurs in t-St
*. Isomerization of c-St
* to t-St
proceeds via
the twisting which is faster in c-St
* than in t-St
* as a result of the interactions between

the Ph groups of c-St. It is suggested that c-St
* and t-St
* exist in potential minima,

that the internal conversion from D
2
to D
0
proceeds with k
ic
c
f
k
ic
t
=(4.05.6) 10
8
sec
1
,
and that only c-St
* undergoes isomerization to t-St
via the twisting with k

i
=(1.0 F
0.3) 10
8
sec
1
. A diabatic process similar to that for the c!t isomerization of c-St
+
* to
t-St
+
* is proposed for the isomerization of c-St
* to t-St
. It is suggested that c-St
* is
twisted at a potential minimum which undergoes a diabatic crossing to t-St
(D
0
) having a
twisting form without a large barrier. On the other hand, a planar t-St
* exists in a
potential minimum with the relatively large barrier for the twisting and undergoes internal
conversion to t-St
(D
0
) having a planar form.
Photoelectron ejection occurs in (St
*)
z
, while c!t isomerization occurs in c-St
*
and c-St
+
*. However, the k
i
of c-St
* is 41 times smaller than that of c-St
+
*, and B
i
of
c-St
* is 3.5 times smaller than that of c-St
+
* (Table 8). k
i
is 5.6 times smaller than k
ic
of
c-St
*, while k
i
is slightly greater than k
ic
of c-St
+
*. The k
ic
of St
* is an order of
magnitude smaller than that of St
+
*. These dierences are responsible for the potential
surfaces of St
(D
2
) and St
(D
0
) and their relations, which are probably dierent from
those of St
+
[138]. It may be considered that the D
2
and D
0
states lie less closely in St
than in St
+
. H =1.0 and 7083 psec for c-St and t-St in the S
1
states have been reported
Figure 17 Transient absorption spectra recorded immediately after e
(o), before (.), and

immediately after (D) hv
532
during PRLFP of c-St (5 10
3
M) and Bp (1 10
1
M) mixture in
DMF. The delay time of hv
532
from e
was 60 nsec.
Figure 18 Kinetic traces illustrating time proles of DO.D.
405
, DO.D.
500
, and DO.D.
520
as a func-
tion of time after e
during PRLFP of mixtures of c-St and Bp. [c-St] = 5.0 10

3
, [Bp]=0 (a), 1
10
2
(b), 2 10
2
(c), 5 10
2
(d), and 1 10
1
M (e). The delay time of hv
532
from e
was 60 nsec.
from S
1
!S
0
uorescence measurement [139145]. It is clearly suggested that the transient
phenomena of M
(D
2
) cannot be assumed on the basis of those of neutral molecules in
the S
1
state or M
+
(D
2
).
In conclusion, Bp acts as a selective electron quencher for St
* via ET quenching.
Assuming that k
et
=k
di
, s
c
and s
t
are estimated to be 1.5 and 2.5 nsec, respectively, which
are longer than s=120 and 240 psec for c-St
+
* and t-St
+
* (Table 8). The order of s
c
<s
t
is attributed to the isomerization via the twisting only in c-St
*, because twisting is
favorable in c-St
* compared with t-St
*. It is suggested that diabatic isomerization

from c-St
* to t-St
proceeds via crossing of the D

2
and D
0
states. On the basis of the
present results, the method can essentially work to determine the lifetimes of any M
* by
the selective ET quenching assuming k
et
=k
di
.
4.3. Lifetime of Radical Anions of Dicyanoanthracene, Phenazine, and
Anthraquinone in the Excited States
The lifetimes of M
*, such as 9,10-dicyanoanthracene (DCA), phenazine (PZ), anthra-

quinone (AQ), and substituted anthraquinones [RAQ=2-methylanthraquinone (2-MAQ),
2-tert-butylanthraquinone (2-BAQ), 1-chloroanthraquinone (1-CAQ), and 2-chloroanthra-
quinone (2-CAQ)], have been measured by the selective ET quenching of M
* by an
electron quencher (Q) during PRLFP in DMF [47].
Selective Electron Transfer Quenching of Radical Anions in the Excited State
The transient absorption spectra of M
recorded at t = 20 nsec after e
showed three
peaks at 510, 640, and 710 nm for DCA
, and one strong peak at 530560 nm for PZ
,
AQ
, and RAQ
. When M
was irradiated with hv

532
at t = 200 nsec after e
, no
Scheme 14 Reactions of c-St
* involving isomerization, ic, and ET quenching.

Table 8 Properties of t-St
+
, c-St
+
, t-St
+
, and c-St
+
in the D
2
States: s,
a
k
ic
k
i
, /
i
, and E
ex
Radical Ions (D
2
) H [nsec] k
ic
[sec
1
] k
i
[sec
1
] /
I
E
ex
[kcal/mol]
t-St
* 2.5 F 1.0 (4.0 F 1.6) 10

8
0 0 48
c-St
* 1.5 F 0.4 (5.6 F 1.7) 10

8
(1.0 F 0.3) 10
8
0.14 F 0.05 45
t-St
+
* 0.24 F 0.05 (4.1 F 1.1) 10
9
0 0 53
c-St
+
* 0.12 F 0.03 (2.9 F 0.7) 10
9
(4.1 F 1.0) 10
9
0.49 F 0.12 50
a
From k
et
s or k
ht
s assuming that k
et
= k
ht
= k
di
with Q = Bp for St
* and AN for St
+
*, respectively.
change occurred in the transient absorption spectra and the time proles. Therefore M
*
converts to M
within hv
532
duration of 5 nsec.
No transient absorption was observed in the range 450740 nm immediately after e
,
while the absorption of DCA
with three peaks appeared and grewuntil t =150 nsec from

exergonic ET from FN
during PRLFP of DCAfumaronitrile (FN) mixture. When

DCA
was irradiated at t = 190 nsec with hv

532
, the transient absorption of DCA
decreased within hv
532
(Fig. 19), as a result of the selective ET quenching of DCA
* by FN
proceeds to yield DCA and FN
at k
et
. Similar ET quenching of PZ
* or AQ
* by FN
and of M
* by p-dicyanobenzene (DCB) was observed. Assuming k

et
= k
di
= 7.2 10
9
M
1
sec
1
in DMF as discussed above, s for M
* was estimated (Table 9). It should be

emphasized that M
* has a nearly equal s of 45 nsec. The three M
* have dierent
characteristics fromeach other in their structure and electronic properties but an equivalent
E
ex
= 4648 kcal mol
1
. E
ex
might be important for s of M
*. The four RAQ
* have
similar s of 1.01.4 nsec, but they are shorter than s for AQ
*. It is suggested that the

substituents have little eect in size (2-MAQ
* vs. 2-BAQ
*), electronic character (2-

MAQ
* vs. 2-CAQ
*), and position (1-CAQ
* vs. 2-CAQ
*) on s but that the internal

conversion from RAQ
* to the ground state is accelerated by the substituents. The

structural character of M
* inuences only s in a series of M
*. Because the energy gaps

between M
* and M
are almost equivalent for AQ and RAQ (Table 9), a shorter s for
RAQ
* than for AQ
* is probably attributed to rotation of the substituents which

accelerate the internal conversion of RAQ
* to RAQ
.
s = 1.04.4 nsec of M
* are comparable with s = 1.5 and 2.5 nsec of c-St
* and t-
St
*, respectively. These indicate that internal conversion of M
* and St
* occurs with
similar k
ic
as the main process. The structural and electronic characteristics of M
* are
much dierent from those of St
*, while E
ex
= 4648 kcal mol
1
for M
* is similar to
E
ex
= 5053 kcal mol
1
for c-St
* and t-St
*. Therefore, E
ex
is the signicant factor for
the rate of internal conversion of M
* to M
.
Figure 19 Transient absorption spectra recorded at t = 190 nsec after e
(before hv
532
, o) and
immediately after (.) and at 100 nsec (D) after hv
532
during PRLFP of DCA (2.5 10
3
M)FN
(5.0 10
1
M) mixture in DMF. Inset: kinetic trace illustrating time prole of DO.D.
510
as a
function of time after e
.
Table 9 Half-Peak Reduction Potential (E
1/2
red
) of M and Q, E
ex
of M
*, Free Energy Changes (D G and D G*) in the ET from Q
to M and from M
*
to Q, s of M
*, k
ic
=s
1
of M
*, f
-M
of M
that Disappeared, and Relative Separation factor (R=k

sep
/(k
et
+k
sep
)) of Solvated Pairs ((M /Q
)
solv
) Based
on 1.0 for (PZ/FN
)
solv
a
E
1/2
red
[V vs. SCE]
M
* Q M Q E
ex
[kcal mol
1
] DG [kcal mol
1
] DG* [kcal mol
1
] H [nsec] k
ic
=H
1
[sec
1
] /
M
R
DCA
* FN 0.89 1.36 48 11 37 4.4 2.3 10

8
0.25 0.71
DCA
* o-DCB 0.89 1.87 48 23 26 4.7 2.1 10

8
0.13 0.40
DCA
* m-DCB 0.89 1.92 48 24 25 5.4 1.9 10

8
0.086 0.27
DCA
* p-DCB 0.89 1.72 48 20 29 5.0 2.0 10

8
0.11 0.34
DCA
* BN 0.89 2.49 48 37 11 0
PZ
* FN 1.23 1.36 46 3 43 4.1 2.4 10

8
0.34 1.0
PZ
* p-DCB 1.23 1.72 46 11 35 4.8 2.1 10

8
nd nd
AQ
* FN 0.87 1.36 48 11 36 4.0 2.5 10

8
0.095 0.42
2-MAQ
FN 1.0 1.36 48 8 39 1.3 7.7 10

8
0.095 0.36
2-BAQ
FN 1.0 1.36 48 8 39 1.4 7.2 10

8
0.10 0.32
l-CAQ
FN 0.83 1.36 48 12 36 1.1 9.1 10

8
0.063 0.28
2-CAQ
FN 0.78 1.36 48 13 34 1.0 1.0 10

9
0.076 0.27
a
DCA = 9,10-dicyanoanthracene, PZ = phenazine, AQ = anthraquinone, 2-MAQ = 2-methylanthraquinone, 2-BAQ = 2-tert-butylanthraquinone, l-CAQ = l-
chloroanthraquinone, 2-CAQ = 2-chloroanthraquinone, FN = fumaronitrile, DCB = dicyanobenzene, and BN = benzonitrile. E
1/2
red
(vs. SCE) was calculated from E
1/2
red
(vs. SCE)=E
1/2
red
(vs. Ag/Ag
)+ 0.25 V, when E
1/2
red
(vs. Ag/Ag
) was given in the reference. DG= E

1/2
red
(Q) E
1/2
red
(M) and DG*=E
1/2
red
(M) E
1/2
red
(Q) E
ex
. /
M
was
measured under the conditions of [M] = 2.5 10
3
, [FN] = 5.0 10
1
, and [DCB] = 3.0 10
1
M. k
sep
and k
et
denote the rate constants of separation to M and Q
and
back electron transfer to M
and Q from (M/Q
)
solv
, respectively.
Intermediacy of Radical Anion-Neutral Molecule Pair in the Electron Transfer
Quenching
As shown in Table 9, u
M
depended on the combination of M
* and Q. u
PZ
in PZ
*FN
was the largest among the M
*Q pairs, while u
AQ
in AQ
*FN was considerably

smaller than u
DCA
in DCA
*FN and u
PZ
in PZ
*FN. u
RAQ
in RAQ
*FN was
comparable with u
AQ
in AQ
*FN, whereas u
DCA
in DCA
*DCB was much smaller

than u
DCA
in DCA
*FN. These results show that the eciency of the disappearance of

M
and the formation of Q
depends on the combination of M
*Q and suggest the

intermediacy of (M/Q
)
solv
in the selective ETquenching of M
* by Q. In other words, ET
proceeds with k
et
to initially give (M/A
)
solv
, with competition of the internal conversion of
M
* to M
with k
ic
. (M/Q
)
solv
separates into Mand Q
at k
sep
or returns to M
and Q
via back ET at k
et
. Because u
M
is proportional to the separation factor of (M/Q
)
solv
,
relative separation factors of R = k
sep
/(k
et
+k
sep
) are calculated on the basis of R=1.0 for
(PZ/FN
)
solv
. As k
sep
of (D
/Q
)
solv
is assumed not to depend on the structures of D
and Q
in photoinduced ET reactions of DQ mixtures, the dierence in R is responsible

for k
et
controlled by DG in (M/Q
)
solv
. Indeed, R has a correlation with DG but not
completely (Table 9). Although electrostatic interaction are preferential for R in (D
+
/
A
)
solv
, structural relations might also be important for R in (M/A
)
solv
.
In conclusion, the selective ET quenching of M
* (M = DCA, PZ, AQ, and RAQ)

by Q (FN and DCB) occurs at k
et
= k
di
because of the large exergonic character. s of
M
* (M = DCA, PZ, and AQ) is estimated to be 4 nsec, while s = 1.01.3 nsec of

RAQ
* is shorter than that of M
*.
5. FLUORESCENCE OF RADICAL CATIONS IN THE EXCITED STATE
Fluorescence spectroscopy has sensitivity as high as up to the single-molecular detection
level. However, uorescence detection of M
+/
has been usually unsuccessful by their

extremely low uorescence quantum yields (u
f
) in solution even if their parent molecules
are highly uorescent. This is attributed to the low E
ex
favorable for internal conversion
and the high chemical reactivity of M
+
*
/
* [33,146,147]. Only a few tens of examples of

uorescent M
+/
have been reported but some of them are quite doubtful [148150].
5.1. Fluorescence of 1,3,5-Trimethoxybenzene Radical Cation (TMB
+
)
Ecient uorescence (u
f
= 1.1 10
3
) of 1,3,5-trimethoxybenzene radical cation in the
excited state (TMB
*) has been observed during excitation of TMB
+
generated from
PET of TMB-1,4-dicyanonaphthalene (DCN)Bp mixture in acetonitrile by two-laser,
two-step excitation technique [147153]. Excitation with a XeCl excimer laser (308 nm, 8
nsec) initiated ET between
1
DCN* and Bp giving DCN
and Bp
+
, which led to the
secondary ET with O
2
and TMB to give O
2
and TMB
+
with a peak at 590 nm,
respectively. Excitation of TMB
+
with hv
532
(6 nsec) gave uorescence spectrum around
620 nm symmetry to the absorption spectrum. u
f
= 1.1 10
3
allowed an estimation of s
= 210 psec using the StricklerBerg relationship, giving k
f
= 9.5 10
6
sec
1
for natural
radiative rate constant of TMB
+
*.
Formation Kinetics of [TMB
+
/Cl
] Ion Pair during PR

Pulse radiolysis of M in chlorinated solvents has been a standard method to generate M
+
due to the high ionization potential (IP) of the solvent molecules [146,154156]. However,
the oxidation process is rather complicated because of the generation of Cl
, which is also
an oxidant together with solvent
+
during PR [125,157160]. Cl
forms complexes or an
ion pair directly with M [157]. In addition, such species is also formed from M
+
and Cl
in the course of their neutralization [161,162]. Therefore observed transient absorption

spectra would be a sum of spectra of free ions and complexes or ion pairs.
Pulse radiolysis of TMB in chlorinated solvents gave TMB
+
with a broad spectrum
peaked at 500 nm during PR of TMB in highly chlorinated solvent such as CCl
4
, CH
2
Cl
2
,
or CHCl
3
, although the absorption spectrum of TMB
+
in acetonitrile showed a sharp
peak at 590 nm during LFP [125,159,160]. The transient absorption spectrum was time-
dependent in DCE (Fig. 20) showing a spectrum similar to that in acetonitrile immediately
after e
and similar to that in CCl

4
at >200 nsec. This spectral change was attributed to
the ion pair ([TMB
+
/Cl
]) formation in DCE. The fast and slow processes for ion pair
formation are considered: trapping of Cl
by TMB within a 5-nsec ash and collision of

TMB
+
and Cl
at k
n
= 3.0 10
11
M
1
sec
1
, respectively.
Fluorescence of Free TMB
+
and [TMB
+
/Cl
] Ion Pair
Generation of M
+/
in solution includes one-electron transfer and should be accompanied

with ion pair formation, e.g., M
+
M
, M
+
anion, etc. in any processes. Absorption
spectroscopy of M
+/
are not suciently sensitive to distinguish ion pair from free ion,
while uorescence spectroscopy is enough sensitive. The u
f
of TMB
+
* can be a measure of
the ratio of free TMB
+
to the ion pair [TMB
+
/Cl
], because the excitation of TMB
+
in
the ion pair would cause no uorescence or weak uorescence through rapid HT quenching
of TMB
+
* by Cl
within the ion pair as compared to free TMB
+
. The u
f
of TMB
+
as a
function of delay time (101000 nsec) decreased rapidly during PRLFP of TMB in DCE
Figure 20 Time-resolved transient absorption spectra observed at 0 nsec (solid line), 100 nsec
(dashed line), and 1 Asec (dotted line) after e
and transient uorescence spectrum of TMB
+
* ob-
served at 300 nsec after e
during PRLFP of TMB (1.0 10

2
M) in DCE. Energy of hv
532
, 130 mJ.
(Fig. 21). The addition of 1.2 10
2
M of tetrabutylammonium chloride as a source of Cl
drastically accelerated the decrease of u

f
, as well as the blue shift of the transient absorption.
u
f
fell into (23) 10
5
within 20 nsec after e
, which would represent the u

f
of [TMB
+
*/
Cl
] and the lowu

f
was attributed to HT quenching of TMB
+
* by Cl
in [TMB
+
*/Cl
]. s
of TMB
+
* in the ion pair in DCE and k
et
for HT quenching of TMB
+
* by Cl
within the
ion pair were estimated to be 3.2 psec and 3.0 10
11
sec
1
, respectively. On the other hand,
free TMB
+
was generated fromHT during PRof TMB in the presence of Bp in DCE. Free
TMB
+
* emits a uorescence with u
f
= 1.1 10
3
.
Free ion fraction in the total ion amount can be estimated from u
f
=u
f
(free ion)+u
f
(ion pair). Pulse radiolysis of TMB (1.0 10
2
M) in DCE gave TMB
+
, whose ion pair
fraction is 50% immediately after e
and 75% at 1 Asec. Possibly fast ion pair formation

could be attributed to the reaction of Cl
with TMB. Fromthe u

f
for TMB
+
* in the ion pair,
we estimated free ion fraction (R
f
=[free TMB
+
]/([free TMB
+
]+[TMB
+
/Cl
]), R
f
=
0.55 at 0 nsec and R
f
=0.2 at 1 Asec after e
during PRof TMB in DCE. u

f
=k
f
/(k
f
+k
ic
+
k
ht
) = k
fs
is represented by k
ic
and k
ht
of internal conversion and HT quenching within the
ion pair, respectively. Therefore, s of free TMB
+
* and TMB
+
* in the ion pair is estimated
to be 116 and 3.2 psec, while the k
ic
and k
ht
were also calculated to be 8.5 10
9
and 3.0 10
11
sec
1
, respectively. The transient behaviors of free TMB
+
* and TMB
+
* in the ion pair are
summarized in Scheme 15.
u
f
= 3.6 10
5
and 1.9 10
4
of TMB
+
* in CCl
4
and CH
2
Cl
2
, respectively, at a
delay time of 100 nsec were also estimated in a similar manner. These results can be
explained by the ion pair formation fromTMB and Cl
in these solvents. This indicates two

mechanisms for the ion pair formation through ET from TMB to Cl
as a fast process and

through the recombination of TMB
+
and Cl
as a slow process.
Figure 21 u
f
of TMB
+
as a function of the delay time of hv
532
relative to e
during PRLFT of
TMB (1.0 10
2
M) (open circle) and Bp (5.0 10
2
M)TMB (1.0 10
3
M) mixture (solid circle)
in DCE.
5.2. Fluorescence of TMB
+
Derivatives and the Quenching
Although the uorescence of the TMB
+
* family was studied [125,159,160], uorescence
was observed only in TMB
+
* among mono-, di-, tri-, tetra-, and penta-methoxybenzenes
and among 1,2,3-, 1,2,4-, and 1,3,5-trimethoxybenzenes. This indicates that 1,3,5-trioxyl
substitution is necessary for the uorescence. Pseudo-D
3h
symmetry cause the degenerate of
the singly occupied and second highest occupied molecular orbitals (SOMO and SHOMO,
respectively) in the TMB
+
family bearing 1,3,5-trioxybenzene structure. Therefore, the
TMB
+
family has low D
0
D
1
and high D
0
D
2
energy separations. This makes the D
2
!D
0
transition radiative enough to compete with D
2
!D
1
internal conversion.
Fluorescence was observed for the TMB
+
* family such as 3,5-dimethoxyphenol,
1,3-dihydroxy-5-methoxybenzene (5-methoxyresorcinol), 1-acetoxy-3,5-dimethoxyben-
zene, and 1,3,5-trimethoxy-2-methylbenzene. These results indicated that complete sym-
metry of the substitution on O atoms is not necessary to observe uorescence from the
TMB
+
* family, and that the variation of parent molecules of uorescent radical cation is
possibly performed [153]. Fluorescence was also detected from hexamethxybenzene
+
* as
an example of pseudo-D
6h
molecules. The discussion of the symmetry has been described
here on the uorescence from uorobenzenes
+
* in the vapor-phase or noble gas matrices.
The u
f
of TMB
+
generated during PR in DCE decreased with the introduction of
alkyl or acetyl substituents at O atoms suggesting that they act as quenchers. For example,
u
f
=2 10
3
, 1.1 10
3
, and c0 for 1,3,5-trihydroxybenzene
+
, TMB
+
, and 1,3,5-
triacetoxybenzene
+
(TAB
+
), respectively. However, the mechanisms involved in the
quenching of 1,3,5-trioxybenzenes
+
* are not the same. Internal conversion promoted by
the CUH vibration would operate in TMB
+
* and intramolecular HT would take place in
TAB
+
*.
Excitation of TMB
+
generated by PR in benzonitrile or in DCE in the presence of
benzonitrile gave weak or zero uorescence as a result of intermolecular HT quenching
[153]. This process has an exothermicity of c0.57 eV estimated from the ionization
potentials (IP) of TMB and benzonitrile (IP=8.11 and 9.62 eV, respectively) and E
ex
of
TMB
+
(2.03 eV). Similarly, uorescence from TMB
+
* was not observed in acetone
Scheme 15 Transient behaviors of free TMB
+
* and [TMB
+
*/Cl
].
(IP = 9.67 eV) and cyclohexane (IP=10.32 eV). On the other hand, uorescence of
TMB
+
* was observed in acetonitrile, DCE, 1,1,1,3,3,3-hexauoro-2-propanole, 2,2,2-
triuoroethanol, and other chlorinated solvents (IP>10.4 eV). The absence of the uo-
rescence from TAB
+
* could be a result of intramolecular HT quenching of the TMB
+
*
family by the acetyl group (IP=10 eV).
5.3. Fluorescence of 3,5-Dimethoxyphenol Radical Cation (DMP
+
)
If strong uorescence of M
+
is found, it will be a uorescent M
+
probe to monitor
ET/HT phenomena in homogeneous and heterogeneous environment with a high sensi-
tivity. DMP
+
showed a uorescence stronger than TMB
+
in DCE [150,163].
A transient absorption spectrum with a peak at 575 nm assigned to DMP
+
was
observed immediately after e
during PR of DMP (5.0 10

3
M) in DCE. The time-
resolved transient absorption spectra showed a slow growth of a new peak at 500 nm
assigned to 3,5-dimethoxyphenoxy radical (DMP
) (Fig. 22). The peak at 575 nm due to

DMP
+
decreased with time, and most of DMP
+
disappeared at 2 Asec after e
to yield
DMP
through deprotonation of DMP
+
. It has been shown that bimolecular deproto-
nation of DMP
+
occurs to yield DMP
at k
H
+=5.5 10
10
M
1
sec
1
in the presence of
basic reagents. The basic species for the deprotonation is probably Cl
generated by the
radiation chemical primary processes of DCE. The plausible mechanism involved therein
is summarized in Scheme 16.
The similarity of the absorption spectrum of DMP
+
to that of TMB
+
indicates a
similar electronic structure. The structure of TMB
+
is deviated frompseudo-D
3h
symmetry
because of repulsion of three Me groups, while that of DMP
+
is closer to pseudo-D
3h
symmetry. When D
3h
symmetry is an important factor for higher eciency of the
uorescence and Me group enhances internal conversion, DMP
+
* uoresces stronger
than TMB
+
*. It is interesting to knowwhether unimolecular deprotonation fromDMP
+
*
Figure 22 Time-resolved absorption spectra measured at 30, 220, and 2000 nsec (gate time: 30 nsec)
after e
during PR of DMP (5.0 10

3
M) in DCE.
competes with the radiative transition or not. If it occurs, the uorescence eciency of
DMP
+
becomes lower than TMB
+
.
Excitation of DMP
+
with hv
532
gave a broad uorescence around 600750 nm
(Fig. 23). The uorescence spectrum showed a mirror image symmetry to the absorption
spectrum of DMP
+
. The integrated uorescence intensity monitored decreased with the
increase of the delay time of hv
532
relative to e
in a similar manner to the temporal prole

of the transient absorption monitored at 575 nm (Fig. 23b). This also supports the
assignment of the uorescence to that of DMP
+
*. When DMP
+
was excited with hv
532
,
the absorption of DMP
+
was unchanged and no increase in that of DMP
was observed.
This indicates that DMP
+
* does not undergo deprotonation, unlike its neutral molecule
[164]. Because the acidity of the OH group of DMP
+
in the ground state is enhanced by
the positive charge of DMP
+
and deprotonation takes place even in the presence of weak
bases such as Cl
or H
2
O, and E
ex
= 47 kcal mol
1
and the resonance stabilization of the
Scheme 16 Deprotonation of DMP
+
through [DMP
+
/Cl
].
Figure 23 Fluorescence spectrum of DMP
+
measured at 100 nsec after e
. Energy of hv
532
, 130
mJ. Inset: a plot of the integrated uorescence intensity of DMP
+
as a function of the delay time of
hv
532
relative to e
(open circle) is superimposed with a plot of DO.D.

575
(solid circle).
DMP
(12 kcal mol

1
) would further enhance the acidity, it is surprising to observe no
spontaneous deprotonation of the OH group of DMP
+
upon excitation. The absence of
the deprotonation upon excitation strongly suggests that MO incorporated in the
excitation of DMP
+
does not correlate with the j* orbital of the OH bond.
The u
f
of DMP
+
in DCE was measured from the uorescence intensity as a function
of the delay time of hv
532
relative to e
and the time dependence of DO.D.

532
. u
f
=(2F0.3)
10
3
was independent of the delay time except for u
f
=1.3 10
3
at 30 nsec. The low u
f
at 30 nsec may have resulted from HT quenching of DMP
+
* by Cl
in [DMP
+
*/Cl
].
u
f
= (2F0.3) 10
3
for DMP
+
* was higher than B
f
= 1.1 10
3
for free TMB
+
* in
DCE. The intense uorescence of DMP
+
* ruled out the demand of complete pseudo-
D
3h
structure in M
+
* and suggested a possibility of substitution of H atom of the OH
group of DMP with an alkyl group as an attachment group for the introduction of DMP
unit to various molecules or surfaces as a uorescent radical cation probe. k
f
= 5.8
10
6
sec
1
was estimated for the uorescence decay of DMP
+
* using the StricklerBerg
relationship. Although k
f
was smaller than that for TMB
+
* (9.5 10
6
sec
1
), u
f
was
larger by a factor of 1.8. It is suggested that internal conversion in DMP
+
* is slower by
a factor of 3.0 as compared to TMB
+
*. Because the deprotonation from DMP
+
* is
not an important process for internal conversion, the Me group would play an important
role in internal conversion of DMP
+
* and TMB
+
* as reported for that of
1
alkylbenzenes*
[165]. sc350 psec of DMP
+
* was estimated from u
f
= k
f
/(k
f
+ k
ic
) = k
f
s c k
f
/k
ic
. It
is strongly suggested that the introduction of Me groups in 1,3,5-trioxybenzenes causes
the deviation from the pseudo-D
3h
structure by their mutual repulsion, reducing u
f
by the
enhancement of internal conversion.
It is found that radical cations of 1,3,5-trixybenzene derivatives in solution uoresce
with moderately high u
f
c10
3
in the rage of 580800 nm.
New aspects of radical ion chemistry in solutions have been described in this chapter.
These studies were performed by PR, g-R, and PRLFP techniques in which M
+
or M
can be selectively generated at 10

5
M.
Remarkable enhancements of the unimolecular ct isomerizationof c-S
+
withp-MeO
and oxidation of S
+
with p-MeO are explained by chargespin separation in such S
+
.
Unimolecular ct isomerization of such c-S
+
proceeds with a chain mechanism, while
regioselective oxidation occurs in such S
+
because of the spin localization. Cycloreversion
of t,c,t-TPCB
+
occurs to give a j-St
2
+
, while the photochemical cycloreversion of t,c,t-
TPCB
+
and t,t,t-TPCB
+
gives k-St
2
+
and t-St
+
/t-St pair, respectively. Radical cations of
phosphorus compounds (9
+
and 10
+
) form intramolecular k-dimer
+
between two Nps
from which Np
2
+
forms. Formation of intermolecular j-dimer
of aromatic acetylene
(11
and 12
) and intramolecular dimer
of 13
and diarylmethanol
was observed,
and the n = 3 rule is not eective for intramolecular dimer
.
Anisole and Bp act as selective hole and electron quenchers for St
+
* and St
+
* via
HTand ETquenching, respectively. Assuming that k
ht
=k
et
=k
di
, s
c
and s
t
were estimated
to be 120 and 240 psec for c-St
+
* and t-St
+
*, respectively, which are shorter than H =1.5
and 2.5 nsec for c-St
* and t-St
*. The order of s
c
<s
t
is attributed to the isomerization
via the twisting only in c-St
+
* and c-St
*, because twisting is favorable in c-St
+*/
*
compared with t-St
+*/
*
. Diabatic isomerization from c-St
*/
*
to t-St
+/
is
suggested to proceed via crossing of the D
2
and D
0
states. The selective ET quenching of
M
* (M = DCA, PZ, AQ, and RAQ) by Q (FN and DCB) occurs to give s = 4 nsec of
M
* (M = DCA, PZ, and AQ) and s = 1.01.3 nsec of RAQ
*. Intermediacy of the
M/Q
pair is suggested during ET quenching of M
* by Q.
It is found that radical cations of 1,3,5-trioxybenzene derivatives such as TMB
+
and
DMP
+
in solution uoresce with moderately high u
f
c10
3
in the range of 580800 nm.
Large u
f
was obtained for free TMB
+
, while small u
f
was obtained for the [TMB
+
/Cl
]
ion pair because of fast HT quenching of TMB
+
* by Cl
in the ion pair generated fromET

from TMB to Cl
and collision between TMB
+
by Cl
. 1,3,5-Trioxyl substitution is
necessary for the ecient uorescence because of the pseudo-D
3h
symmetry causing low
D
0
D
1
and high D
0
D
2
energy separations. Intramolecular and intermolecular HT
quenching of TMB
+
* occurred by substituents of the O atom and hole acceptor molecules
with low IP.
Because M
+
*
/
* has spin, charge, and E

ex
, chemistry of M
+
*
/
* is interesting and
still a new subject. The PR method can allow us to study various M
+/
as the starting
molecule. Because we used the 532-nmlaser ash for excitation of M
+/
in this study, only

M
+/
with absorption at 532 nmcan be used as the starting molecule. When we can use any
k for LFP, various M
+/
can be excited at k tuned to the absorption of M
+/
. And
because various excited states exist in M
+
*
/
*, selective excitation of M
+/
to M
+/
(D
n
) is of particular interest to elucidate the transient phenomena depending on the
excited state. Although it has been considered that M
+
*
/
* is nonluminescent, we have
found that 1,3,5-trioxybenzenes
+
uoresces with moderately high u
f
c10
3
. Considering
that uorescence was readily observed with conventional photomultiplier as a detector,
we can expect the use of these type of compounds as ET/HT probe for homogeneous
solutions and also for heterogeneous systems such as photocatalysts, and biological
oxidation in future.
ACKNOWLEDGMENTS
The author thanks his collaborators, particularly Mrs. Sachiko Tojo, Drs. Akito Ishida,
Nobuyuki Ichinose, Mitsunobu Nakamura, and his students, as well as the members of
the Radiation Laboratory of ISIR, Osaka University, for running the linear accelerator.
This work was partly supported by a Grant-in-Aid from the Ministry of Education,
Culture, Sports, Science and Technology (MEXT) of Japanese Government.
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23
Application of Radiation Chemistry
to Nuclear Technology
Yosuke Katsumura
The University of Tokyo, Tokyo, Japan
INTRODUCTION
Nuclear technology is dened as a technology to use the nuclear energy through nuclear
ssion and fusion reactions as nuclear power and to develop useful processing and
application with radiation and radioisotopes. Therefore radiation-induced eect is one of
the important issues when nuclear technology is developed and employed. In the present
chapter, three important applications of radiation chemistry in nuclear technology will be
discussed: coolant water in nuclear power stations, spent nuclear fuel reprocessing, and
radioactive high-level waste repository.
1. RADIOLYSIS OF WATER AT ELEVATED TEMPERATURERADIATION
EFFECT OF COOLANT WATER IN NUCLEAR REACTORS
1.1. Importance for the Understanding of the Radiolysis at Elevated
Temperatures
All over the world, 432 nuclear power reactors are under operation and more than 36 GWof
electricity could be produced as of December 31, 2001. There are several types of reactors
such as boiling water reactor (BWR), pressurized water reactor (PWR), Canada deuterium
uranium(CANDU), and others. In these reactors, light water is normally used not only as a
coolant, but also as a moderator. On the contrary, in CANDU reactors, heavy water is
taken. It is widely known that the quality control of coolant water, the so-called water
chemistry, is inevitably important for keeping the integrity of the plant.
The coolant water at around 300jC is irradiated by both g-rays and fast neutrons at
the core region with a dose rate of several 10 kGy/sec, which is more than 3 orders of
magnitude of the dose higher than those obtained in conventional
60
Co g-ray irradiation
facilities. As a result, O
2
and H
2
O
2
are formed as radiolysis products. It is well known that
the concentrations of O
2
and H
2
O
2
strongly aect the stress corrosion cracking (SCC) and
the electrochemical corrosion potential of the primary circuit. In order to avoid the SCC, it is
necessary to keep the lower level of these concentrations and hydrogen injection (HWC),
and, recently, noble metal chemical addition (NMC) has been widely employed in BWRs. In
the hydrogen injection, both H
2
O
2
and O
2
would be converted into water molecules by
radiolytic processes (see below).
To grasp the chemical condition of water in the pressure vessel, direct measurement is
practically impossible because of high pressure, high temperature, and intense radiation. In
order to predict the concentrations of water decomposition products, a computer simulation
should be applied. This idea was found in 1960s [13]. To performthe simulation, both a set
of G-values for water decomposition products and a set of reactions for transient species are
necessary. For these two decades, much eort has been made in Sweden, Denmark, United
Kingdom, Canada, and Japan to evaluate the G-values and rate constants of the reactions at
elevated temperatures up to 300jC, and nowthere are practically enough accumulated data.
There are several reviews of water radiolysis at elevated temperatures [47] and examples of
practical application of the radiolysis in reactors [8,9].
1.2. Temperature Dependence of Water Decomposition Products
up to 300jC
The coolant water at around 300jC is irradiated mainly at the core of the reactor. At the
initial stage to determine the G-values of water decomposition products at elevated
temperatures, the Fricke dosimeter was chosen [1014] because the mechanism of the
reaction has been established. Since the reactions in neutral solution are of practical interest,
intensive measurement of the G-values of water decomposition products at elevated
temperatures in neutral solutions has been done [1521].
For the measurement, techniques of product analysis and pulse radiolysis were
employed. In product analysis, H
2
yield in degassed 2 mM KBr or 1 mM KNO
2
solutions
were taken to evaluate g(H
2
) and degassed solutions of 1 mM Cd
2+
with 10 mM methanol,
1 mMacetone with 10 mMmethanol, and 1 mMacetone with 10 mM2-rpropanol have been
selected for g(H)+g(H
2
). For the measurement of g(e
aq
)+g(H)+g(H
2
), degassed solution
of 1 mM HClO
4
with methanol was taken. In pulse radiolysis measurement, Fe(CN)
6
3
and
CO
3
were used for g(OH) evaluation and 0.25 mM methyl viologen solution with 10 mM
tert-butanol for g(e
aq
). Many other systems have been used. In the presence of formate, the
yield of G(MV
+
) would be equal to g(e
aq
)+g(H)+g(OH). Here g(X) indicates the primary

yield of water decomposition product X and G(Y) is corresponding to the experimentally
determined yield of species Y.
The scavenging capacity is dened as the product of the rate coecient of the sca-
venging reaction and the scavenger concentration. The inverse of the scavenging capacity is
equal to the lifetime of the reactive species. The scavenging capacity for the transient species
at room temperature in each solution is 10
7
sec
1
. In other words, these values are
corresponding to the yields of the transients in the time range of 100 nsec. With increasing
temperature, the reactivity of the scavenger would be accelerated and dependent on the kind
of scavenger. However, experimental data using dierent scavengers do not showsignicant
dierence. Furthermore, at elevated temperatures, the time range where the yield was de-
termined is not clearly shown yet because the rate constants of the reactions are not precisely
known.
Reported values as a function of temperature are summarized in Fig 1 [1720,2224].
In spite of the experimental error, temperature dependence is similar among the evaluations.
The G-values of e
aq
and OH are increasing with increasing temperature. On the contrary,

the value of H
2
O
2
is decreasing. The value for H
2
tends to increase slightly. Elliot et al. [19]
proposed the tting equations as follows.
ge
aq
2:56 3:40 10
3
t 1
gOH 2:64 7:17 10
3
t 2
gH
2
0:43 0:69 10
3
t 3
gH
2
GH 0:97 1:98 10
3
t 4
gH
2
O
2
0:72 1:49 10
3
t 5
Here t stands for temperature in jC.
Fromthe dierence between Eqs. (4) and (3), the temperature dependence of g(H) can
be calculated as
gH 0:54 1:28 10
3
t 6
These lines are also drawn in Fig. 1. It is clear that the agreement is quite nice. Similar tting
equations in heavy water for CANDU reactors were also obtained [19]. Furthermore,
temperature-dependence measurements with fast neutrons and high LET ion beams were
also investigated [20,23].
Common features of water radiolysis at elevated temperatures up to 300jC are
summarized as below.
1. g(e
aq
), g(OH), g(H
2
), and g(H) are all increasing almost linearly with increasing
temperature up to 300jC. About 40% increase was found for g(e
aq
) and more
than 80% for g(OH). This is due to the lower reactivity of OH as compared with
that of e
aq
at elevated temperatures.
2. g(H
2
O
2
) is decreasing with temperature. In spite of the short lifetime of H
2
O
2
due to the thermal decomposition, 50 min at 150jC, 510 min at 150jC, and 1
min at 200jC, this decrease is obvious.
As pointed out before, time scale of scavenging, corresponding to G-values at elevated
temperatures, is not clear yet and further investigation is needed.
1.3. Rate Constants of the Reactions up to 300jC
It is known that more than 30 reactions are needed to reproduce the radiation-induced
reactions occurring in pure water. Intensive measurements with a pulse radiolysis method
have been done at elevated temperature up to 300jC [2542], and the temperature depend-
ence of some reactions does not exhibit a straight line but a curved one in Arrhenius plot.
These examples are the reactions of the hydrated electron with N
2
O, NO
3
, NO
2
, phenol,
SeO
4
2
, S
2
O
3
2
, and Mn
2+
[33,35], and two examples, e
aq
+NO
3
and e
aq
+NO
2
, are shown in
Fig. 2. The rate constant for the reaction of hydrated electron with NO
3
is near
diusion-controlled reaction at roomtemperature and is increasing with increasing temper-
ature. Above 100jC, the rate does not increase and reaches the maximumat 150jC, and then
decreases. Therefore the curve is concave upward in Arrhenius plot.
Figure 1 Variations of G-values (in aprt./100 eV) for the radiolysis of light water as a function of
temperature; (a) reducing species G-values for G(e
aq
), G(H+H
2
), and G(H
2
) and (b) oxidizing
species. Data are taken from Ref. 19 (o5 w q), Ref. 18 (.Ex), and Refs. 20 and 23 (6) for reducing
species and from Ref. 19 (w .o), Ref. 17 (65), and Ref. 24 (Dxj) for oxidizing species. It is noted
that because of the large uncertainties in the G-values determined in Refs. 20 and 23 for both G(OH)
and G(H
2
O
2
) from HClO
4
+10
2
mol kg
1
methanol chemical system at above 100jC, these data are
not shown in (b). Lines are corresponding to Eqs. (1)(5).
Figure 2 The Arrhenius plot rate constants for the reactions of e
aq
with NO
3
(a) and NO
2
(b):
k
obs
(n), k
react
(.), k
di
(
: : :
), calculated t of k
react
(). A
1
/M
1
and A
2
are (5.7F2.1) 10
12
and (4.4
F 6.0) 10
5
, respectively, for (a). A
1
/M
1
and A
2
are (2.0 F 0.8) 10
11
and (2.1 F 0.7) 10
3
,
respectively, for (b). (From Ref. 35.)
In general, observed reaction rate constant is written as below with a diusion term
and a reaction term [43].
1=k
obs
1=k
di
1=k
react
7
The reaction of the hydrated electron would be considered as a charge transfer reaction and
elementary processes can be described as below [44].
D AZ
K
A
D=AZ
k
1
k
2
D=A*Z
m
D
=A
*!
k
3
D
=A
! product 8
Based on the above scheme, an equation for the overall reaction is derived and setting k
3
=k
2
gives a next one [44].
k
react
K
A
k
1
=2 k
2
=m 9
This is rearranged into Eq. (10)
k
react
T A
1
expE
1
=RT=2 A
2
expE
2
=RT 10
Here K
A
k
1
= A
1
exp(E
1
/RT) and k
2
/m = A
2
exp(E
2
/RT).
The temperature dependence of k
di
can be evaluated by the diusion coecients of
the reactants as a function of temperature. The term of k
obs
is experimentally observed.
Then, k
react
can be evaluated by tting procedures. In Fig. 2, k
obs
, k
di
, and k
react
were all
shown [35]. Similar analysis was made for the experimentally obtained reactions of OHwith
Fe(CN)
6
4
, OH, and HCO
2
, H with MnO
4
and O
2
, e
aq
with H
+
, H
2
O
2
, and Cd
2+
, and
so on [34,37,42].
Recent measurement of the hydrated electron at elevated temperature by Shiraishi
et al. [41] shows clearly the existence of an equilibrium between the hydrated electron and
the proton.
e
aq
H
ZH; 11
In order to calculate the reactions in pure water at elevated temperatures, more than 30
reactions as a function of temperature are needed, especially for the reactions in nuclear
reactors. Much work has been done and a reaction set for calculation at 285jCand 300jCis
summarized in Table 1 [4] for light water and in Ref. 5 for heavy water.
1.4. Theoretical Calculations of High-Temperature Radiolysis of Water
In order to reproduce the temporal behavior of water decomposition products, two theo-
retical approaches based on spur diusion model and Monte Carlo calculations have been
developed.
In the spur diusion calculation, initial distribution of the water decomposition after
thermalization is assumed as a spherical one and is set normally as a Gaussian distribution
where hydrated electron has a radius of 2.3 nm, which is larger than the radii of 0.85 nm for
OH, H, H
3
O
+
, H, H
2
, and H
2
O
2
at ambient temperature. Then, the spur reactions start
taking place after 1 psec during the diusion of each species. These calculations have
explained and predicted well the time dependence of the water decomposition products at
roomtemperature. This method was successfully applied to the calculation for the radiolysis
with high LET radiation, where a cylindrical initial distribution is taken. Essence of the idea
has been clearly summarized by Draganic and Draganic [45]. This calculation has been
extended to the water radiolysis at elevated temperatures. Although the initial yields of
water decomposition products at 1 psec are xed as room temperature, the initial dis-
Table 1 Calculated Rate Constants for all Reactions in the Radiolysis of Light
Water at 25jC, 285jC, and 300jC
No. Reaction k
25
k
285
k
300
(1) e
aq
+e
aq
! 6.44E09
a
2.93E11 3.29E11
(2) e
aq
+H! 2.64E10 3.68E11 3.98E11

(3) e
aq
+OH! 3.02E10 1.34E11 1.40E11

(4) e
aq
+H
2
O
2
! 1.41E10 2.53E11 2.76E11
(5) e
aq
+O
2
! 1.79E10 2.57E11 2.78E11
(6) e
aq
+O
2
! 1.28E10 1.65E11 1.78E11

(7) e
aq
+HO
2
! 1.28E10 1.65E11 1.78E11
(8) H+H! 5.43E09 9.20E10 1.00E11
(9) H+OH! 1.53E10 6.58E10 6.87E10
(10) H+H
2
O
2
! 5.16E07 1.03E09 1.13E09
(11) H+O
2
! 1.32E10 9.72E10 1.03E11

(12) H+HO
2
! 9.98E09 7.33E10 7.78E10
(13) H+O
2
! 9.98E09 7.33E10 7.78E10
(14) OH+OH! 4.74E09 2.00E10 2.09E10
(15) OH+H
2
! 4.15E07 1.26E09 1.40E09
(16) OH+H
2
O
2
! 2.87E07 5.42E08 5.91E08
(17) OH+HO
2
! 1.08E10 3.10E10 3.20E10
(18) OH+O
2
! 1.10E10 8.44E10 8.97E10

(19) HO
2
+HO
2
! 6.64E05 2.41E07 2.69E07
(20) HO
2
+O
2
! 7.58E07 3.82E08 4.01E08

(21) O
2
+O
2
! 3.50E07
Equilibria
(22) H
2
O! 1.95E05 7.57E02 6.90E02
(22) H
+
+OH
! 1.10E11 9.76E11 1.07E12

(23) H
2
O
2
! 7.86E02 4.40E01 4.15E01
(23) H
+
+HO
2
! 4.78E10 5.42E11 6.12E11

(24) H
2
O
2
+OH
! 1.27E10 1.37E11 1.47E11

(24) HO
2
+H
2
O! 1.36E06 1.31E08 1.39E08
(25) H! 6.32E00 1.36E05 1.40E05
(25) H
+
+e
aq
! 2.25E10 4.31E11 5.15E11

(26) e
aq
+H
2
O! 1.57E01 8.28E03 9.94E03
(26) e
aq
+OH
! 2.49E07 3.40E10 4.22E10

(27) OH! 7.86E02 4.40E01 4.15E01
(27) H
+
+O
! 4.78E10 5.42E11 6.12E11

(28) OH+OH
! 1.27E10 1.37E11 1.47E11

(28) O
+H
2
O! 1.36E6 1.31E08 1.39E08
(29) HO
2
! 7.14E05 2.70E05 1.98E05
(29) H
+
+O
2
! 4.78E10 5.42E11 6.12E11

(30) HO
2
+OH
! 1.27E10 1.37E11 1.47E11

(30) O
2
+H
2
O! 1.36E06 1.31E08 1.39E08
Alkaline solution
(31) O
+H
2
! 1.21E08 1.62E09 1.75E09
(32) O
+H
2
O
2
! 5.53E08 1.04E10 1.13E10
(33) OH+HO
2
! 8.29E09 1.56E11 1.70E11
(34) O
+OH! 7.60E09 3.23E10 3.38E10

(35) e
aq
+HO
2
! 3.50E09 6.33E10 6.90E10
(36) e
aq
+O
! 2.31E10 1.02E11 1.07E11

(37) O
+O
2
! 3.70E09 3.04E10 3.24E10
(37) O
3
! 2.68E03 1.45E07 1.88E07

The unit for the second-order reactions is M
1
sec
1
and, for the rst order, they are sec
1
. For a
reaction between like species, the value of k, not 2k, is given.
a
Read as 6.44 10
9
.
Source: Ref. 4.
tribution would be varied as a function of temperature. In addition, the rate constants
dependent on temperature were also taken into consideration. In the rst attempt by
Pimblott and LaVerne, the radius for the hydrated electron changes as a function of
temperature was assumed to be expressed with a certain activation energy and compared
with experimental results. The activation energy of 9.6 kJ/mol was selected to reproduce the
experimental data [46]. Swiatla-Wojcik and Buxton [47] considered that the radii are
changed according to the density change of water at elevated temperature. These calcu-
lations could reproduce the yields of water decomposition products up to 300jC for
radiolysis with low LET radiation. Swiatla-Wojcik and Buxton extended the calculation
for high LET radiation and for heavy water [48,49].
The Monte Carlo calculation is a stochastic approach, while the spur diusion
calculation has been classied as a deterministic approach. The most important dierence
is that, contrary to the concentration gradient playing an essential role in spur diusion
calculation, the stochastic nature of the reactions is taken into consideration. In the Monte
Carlo calculation, the initial distribution is derived from the cross-section data between
electrons and water molecules, thermalization distance, and geminate recombination cross
section. The latter two parameters are hardly predicted from theory and are taken as
adjustable ones. Once the initial distribution is xed at 1 psec time, mutual diusion and
reaction processes are calculated with the aid of independent reaction time method [5055].
This calculation has been developed by several groups and has been applied to radiation
biology especially to the radiation damage of DNA [56]. The Monte Carlo calculation has
been applied to the high-temperature radiolysis by Jay-Gerin et al. and could reproduce well
the experimentally evaluated water decomposition products as a function of temperature up
to 300jC and LET dependence [5761].
Both calculations are able to reproduce well the experimental results for high-tem-
perature radiolysis. While in the spur diusion model the initial distribution becomes
broader with increasing temperature, the thermalization distance becomes smaller in Monte
Carlo simulation. Although it seems contradictory, it is dicult to explain the origin of the
dierence.
1.5. Above 300jC and Supercritical Water
Above 374jC and 22.1 MPa, liquid and gas phase of water are merged into a single phase
called supercritical water, as shown in the phase diagram of water (Fig. 3). The property of
the supercritical water is very dierent fromthat of water at roomtemperature. Its density is
dependent on pressure, for example, at 400jC, 0.166 g/cm
3
under 25 MPa and 0.475 g/cm
3
under 35 MPa. The dielectric constant of water at room temperature is 79, but, in
supercritical state, the value is less than 10. Thus the supercritical water is not a highly
polar solvent anymore. In fact, in supercritical state, water can be mixed with benzene at any
composition. On the contrary, inorganic acid, alkaline, and salt compounds have much
lower dissociation constant in higher temperature and in the critical one. At room temper-
ature, hydrogen bonds are expanded all over the water molecules. However, the hydrogen
network is broken in supercritical water and there exist monomers and dimers. Further-
more, pK
w
of water becomes large and also strongly dependent on temperature and pressure
in supercritical condition. By using the above peculiar property, many possible applications
of supercritical water have been proposed. Supercritical water oxidation (SCWO) received
much attention and intensive development has been done because hazardous organic
compounds such as polychlorobiphenyl (PCB) are quickly and completely decomposed
into CO
2
, H
2
O, and Cl
in supercritical water in the presence of oxidant like O

2
or H
2
O
2
.
This can be used for the decomposition of chemical weapons. Another application is that the
supercritical water is a special reaction medium to synthesize the new advanced materials
and medicines. There appeared several reviews on the chemistry and application of super-
critical water [6266].
Recently, a new concept of nuclear reactor using supercritical water as a coolant has
been proposed by a group of the University of Tokyo [67], and this was selected a
Generation IV reactor by DOE in the United States. First pulse radiolysis work was
reported by Ferry and Fox in 1998 [68] and 1999 [69]. Then, in 1999, two more groups at the
University of Tokyo [70] and Argonne National Laboratory [71] started the pulse radiolysis
work on supercritical water. Of course, the main purpose of the study is to evaluate the G-
values of water decomposition and to obtain the rate constants for the reactions in
forthcoming supercritical water-cooled reactors. However, the study has much interest
fromthe viewpoints of radiation chemistry and practical applications because the radiation-
induced reaction would be aected by the change of the dielectric constant of water and
the reaction of OH plays a key role for SCWO. Thus the assessment of the OH radical
in supercritical water provides basic data to practical application of SCWO. Further,
the results obtained in supercritical water would provide good subjects for theoretical
consideration.
For pulse radiolysis study of supercritical water, a specially designed experimental
system is taken as shown in Fig 4. The sample solution is pumped out by using an HPLC
pump and the solution temperature is raised at a preheater and the solution attains the
desired temperature in an irradiation cell. The cell has two optical windows made of sapphire
in place of quartz, which cannot be used because of insucient strength and high solubility
at supercritical water condition. The solution passing through the cell is cooled down and
going to a drain through a back-pressure regulator. The cell is made of Hastelloy, a Ni-based
alloy, which is resistant to corrosion of supercritical water.
The hydrated electron is one of the main water decomposition products, and it is
known that the absorption band of the hydrated electron shifts to longer wavelength with
Figure 3 The phase diagram of water. Critical temperature and pressure of light water, H
2
O, are
374jC and 22.1 MPa.
increasing temperature [7274]. Behavior of the hydrated electron has been investigated
above 300jC and in supercritical water [70,71,75]. The spectrum shift continues beyond
300jC, and its peak is placed at around 1200 nm in supercritical water. Under 25 MPa, the
change of the absorption spectrum of the hydrated electron as a function of temperature is
shown in Fig. 5(a) [76]. In supercritical uids, even when the temperature is xed, the density
varies with changing pressure. At xed temperature of 380jC, the change of the absorption
at dierent pressure conditions is shown in Fig. 5(b) [76]. It is clear that the spectrum is
strongly dependent on temperature and pressure in supercritical water. This is strongly
related to the solvation structure of the hydrated electron and the number of the surrounding
water molecules. However, precise analysis would be a future subject. Separated evaluation
of G-value or absorption coecient of the hydrated electrons through this measurement
seems impossible because only the product of G and absorption coecient (e) can be
determined through the optical measurement. Only when the value of G or e is known
separated evaluation becomes possible. It is noted that the above data were obtained mainly
in heavy water (D
2
O) and not in light water (H
2
O). The light water has an absorption band
above 1200 nm, and it is not easy to do the absorption measurement above 1200 nm. On the
contrary, the D
2
O is transparent up to 1600 nm. The critical temperature and pressure for
D
2
Oare 643.9 Kand 21.7 MPa, respectively, not quite dierent fromthose of H
2
O: 647.1 K
and 22.1 MPa [77].
Other transient radicals such as (SCN)
2
[78], carbonate radical (CO
3
) [79], Ag
0
and
Ag
2+
[80], and benzophenone ketyl and anion radicals [81] have been observed from room
temperature to 400jC in supercritical water. The (SCN)
2
radical formation in aqueous
solution has been widely taken as a standard and useful dosimeter in pulse radiolysis study
[82,83]. The lifetime of the (SCN)
2
radical is longer than 10 Asec at room temperature and
becomes shorter with increasing temperature. This dosimeter is not useful anymore at
elevated temperatures. The absorption spectrum of the (SCN)
2
radical again shows a red
shift with increasing temperature, but the degree of the shift is not signicant as compared
with the case of the hydrated electron. It is known that the (SCN)
2
radical is equilibrated
with SCN
, and precise dynamic equilibration as a function of temperature has been ana-

lyzed to reproduce the observation [78].
Figure 4 Schematic diagram for the pulse radiolysis of supercritical water and cell structure.
The carbonate radical has been measured up to 300jC, and the temperature-
independent spectrum is known [19]. This independence is kept up to 400jC into super-
critical water. Formation and decay behavior were measured precisely [69], and a dimer
model for the carbonate radical has been proposed [79].
Benzophenone solution was taken because it is stable in supercritical water at 400jC.
It is known that the reaction of hydrated electron with benzophenone produces an anion,
Figure 5 (a) Hydrated electron spectrum in D
2
O at 250 bars at increasing temperature and (b)
hydrated electron spectrum in D
2
O at dierent pressure at 380jC. (From Ref. 76.)
and this anion is equilibrated with ketyl radical with pK
a
of 9.2 or 9.25 at roomtemperature
[8486].
/
2
CO e
aq
! /
2
CO
12
/
2
CO
Z/
2
C
OH 13
Therefore adjustment of pHcan control the chemical form. Both spectra of anion and ketyl
radical were measured at dierent temperatures up to 400jC. The spectrum of the anion
shows red shift, but the ketyl radical indicates blue shift.
Apulse radiolysis of Ag
+
solution was studied, and the behavior of formed silver atom
(Ag
0
) and dimer cation (Ag
2
+
) was measured [80]. The absorption band for dimer shows
a signicant red shift with increasing temperatures, which implies to the CTTS (charge
transfer to solvent) character of the band.
It is common that the absorption bands are normally dependent on temperature, and
most of them show red shift at elevated temperatures. These behaviors are closely related to
the solvation and the formation of hydrogen bonds between transients and water molecules.
Precise theoretical consideration is not made yet.
As mentioned before, the spectroscopic behavior of the transients is strongly depend-
ent on temperature and absorption coecients are not constant with temperature. At
present, it is dicult to evaluate the G-values of water decomposition products at elevated
temperatures. One of the recent attempts for the evaluation with a use of methylviologen
(MV
2+
) is shown in Fig. 6 [87]. The methylviologen has been taken to evaluate the G-values
up to 200jC [16,31]. Similar method was applied to higher temperatures up to 400jC
assuming that the absorption coecients would be estimated by extrapolation of the data
known up to 200jC. As shown in Fig. 6(a), the G-value of hydrated electron is increasing up
to 300jC, which is consistent with reported as described as summarized in Fig. 1. The value
is decreasing above 300jC, and above critical temperature, 374jC, a signicant pressure-
Figure 6 (a) g(e
aq
) as a function of temperature at 250 bars and (b) g(e

aq
) as a function of density
at 400jC. (From Ref. 86.)
dependent yield was observed, as shown in Fig. 6(b). When ethanol is taken as a scavenger,
the ethanol radical reduce MV
2+
and the G(MV
) is equal to g(OH)+g(H)+g(e
aq
). It is
evident that not only temperature but also pressure, in other words, density of water, are the
key parameters.
As for the rate constants above 300jC, little experimental results have been reported.
Again, not only temperature, but also pressure dependence was reported. One of the
important issues is the decrease of the dielectric constant of water in supercritical water,
where it is less than 10 and much lower than the value of 79 at room temperature. It was
pointed out that the Coulombic interaction becomes important and the radiolysis of
supercritical water resembles that of the organic liquids with low dielectric constant [88].
In addition, it should be noted that the solubility of the solute is quite low and ion pairing
would have a signicant role [8991], which reects the diculties for the sample prepara-
tion in the actual experiment.
Above observations are the special aspects of the peculiarity of water radiolysis in
supercritical water and thus much further investigation is needed.
2. RADIATION EFFECTS IN SPENT NUCLEAR FUEL REPROCESSING
2.1. Purex Process
In nuclear power reactors, ssion reactions of U-235 are taking place continuously and
energy of 200 MeV per ssion is released. At the electric power plants, ssion energy is
converted into thermal energy at rst and nally to electricity. In commercial reactors, after
the operation for a certain period, new UO
2
fuel is introduced in place of the old one. The
used nuclear fuel is called spent fuel and it is composed of 950 kg U, 9 kg Pu, 75 g Np, 140 g
Am, 47 g Cm, and 31 kg ssion products (FPs) in 1 t of UO
2
after the output of 30 GWday/t
[92]. This composition is a typical one and dependent on both the operation history of the
reactor and the storage time of the fuel after taking out from the reactor. If Pu is separated
from the spent fuel and used as fuel again, high utilization of the fuel is attained. Chemical
processing for the separation of ssile material and removal of the FPs fromthe spent fuel is
called reprocessing. Therefore the main purposes of commercial reprocessing are (1) to
increase the available energy from ssile and fertile atoms and (2) to reduce hazards and
costs for handling the high-level wastes. Two other reasons are sometimes mentioned: (3) to
reduce the cost of thermal reactor fuel cycle and (4) to extract valuable by-products fromthe
high active waste. While several reprocessing methods have been proposed, the Purex
process is the most popular one and has been widely used all over the world. The Purex is an
abbreviation of plutonium uranium rening by extraction, which employs tributyl phos-
phate, TBP, with (C
4
H
9
)
3
PO
4
as an extractant. Since the TBP is rather viscous with a
density of 0.973 g/cm
3
, in an actual process, a 30-vol.% solution in dodecane (n-C
12
H
26
) or
kerosene as a diluent is employed. The mixture solution makes a quick separation of
the organic phase from aqueous phase and exhibits proper viscosity for extraction process.
The spent fuel is dissolved into highly concentrated nitric acid, and UO
2
2+
and Pu
4+
are the
chemical forms for Uand Pu, respectively. After the mixing of organic solvent and aqueous
phase containing dissolved spent fuel, both UO
2
2+
and Pu
4+
in aqueous phase are selec-
tively extracted from aqueous phase to the organic phase and the FPs remain in aqueous
phase. This step is called extraction. Next step is a separation of Pu from organic phase.
After reduction of Pu
4+
to Pu
3+
by chemical or electrochemical method, Pu
3+
goes back to
the aqueous phase selectively, while UO
2
2+
remained in organic phase, which is called
partition. These processes are precisely explained in textbooks [92,93].
The extractant should satisfy several requirements as follows: (1) high distribution
coecient for U and Pu; (2) low distribution coecient for FPs; (3) fast attainment to
equilibrium; (4) stability to water and acid; (5) radiation resistance; (6) low price; (7) low
ammability; (8) big density dierence fromwater; and (9) appropriate viscosity and surface
tension. The mixture of TBP in n-dodecane satises the above requirements and thus has
been widely employed as an extractant in the Purex process. Since the processes are operated
under strong radiation eld not only of g- and h-rays but also of a-rays, degradation of the
solvent takes place and the following detrimental eects appear: (1) loss of Uand Pu; (2) low
decontamination factor (DF) for U and Pu product; (3) lower extraction eciency such as
precipitation, long separation time, the third phase, and emulsion formation; (4) lower
eciency of the process; and (5) instability and danger of the process due to the criticality.
Therefore the understanding of the solvent degradation is inevitable to keep the integrity of
the plant and thus much work has been conducted.
In the eld of the reprocessing, radiation energy released from radionuclides in the
solution is normally expressed in a unit of W hr/1. If all the energy is absorbed in the
medium, the absorbed dose can be calculated as:
1 W hr=1c3600 J=kg 3600 Gy: 14
2.2. Radiolysis of TBP and n-Dodecane
Radiolysis of TBP has been investigated and reported from the 1950s. The main products
are dibutyl phosphate (DBP), monobutyl phosphate (MBP), and gaseous H
2
. Therefore CO
bond scission occurs easier than CC bond scission. The G-value of DBP is higher than
G(H
2
). TBP dimer as a polymeric product is also observed. In addition, other minor
products such as butane, butene, C
1
C
3
hydrocarbons, phosphoric esters, and butanol are
also observed. Reported G-values of TBP radiolysis products are summarized in Table 2
[9498]. The values are scattered probably because of the dierence of the TBPpurity in each
experiment. From ESR measurement of irradiated phosphades alkyl (R), alkylphosphade
[(RO)(R
O)POO
], phosphoranyl [((RO)
2
POO
], and phosphonyl [(RO)POO
] radi-
cals have been observed [99101]. Pulse radiolysis study reported the observation of the
solvated electron in TBP liquid at lower temperatures: at 198 K, the peak position is 1580
nm. The position is shifted shorter wavelength with increasing temperature and the peak
position of 1280 nmwas observed at 223 K[102]. It was found fromthe scavenger eect that
the solvated electron reacts with TBP leading to alkyl radical and DBP:
e
sol
C
4
H
9
O
3
P O !
C
4
H
9
C
4
H
9
O
2
POO
15
Geminate recombination process and reactivity and spectroscopic character of the solvated
electron in a variety of phosphates were also investigated [103,104].
It is noted that the decomposition of TBP takes place not only through radiolysis, but
also through chemical degradation. In chemical degradation, pyrolysis, oxidative decom-
position, and hydrolysis play important roles. Above 150jC, the pyrolysis reaction takes
place and the CObond is broken to lead DBP and MBP formation. The POscission is also
occurring but minor. The oxidation reaction proceeds quickly in 5 M HNO
3
at 75jC,
leading to NO
x
. In the presence of uraniumsalt, this reaction is accelerated and UO
2
(NO
3
)
2
is formed, followed by the formation of butane, butene, N
2
, NO
2
, CO, CO
2
, NO, butyne,
and butanol. It is known that the accidents at Savannah River in 1953 and Oak Ridge in
1959 were triggered by this oxidation reaction. The hydrolysis reaction of TBP occurs in
alkaline, acid, and organic phases leading to DBP and MBP. The diluent will react with
HNO
3
leading to the formation of carboxyl acids, nitric acid ester, and nitro and nitroso
compounds. Rate parameters for chemical degradation under dierent conditions have been
investigated [106,107]. The reaction of n-dodecane with HNO
3
is quite slow.
Radiolysis of hydrocarbons has been investigated and there is a review [108]. n-
Dodecane is one of the saturated hydrocarbons, and its radiation degradation is rather
known as compared with that of TBP. Main degradation products are H
2
and dimers, as
summarized in Table 3 [109,110]. Again, the values are dependent on the reports. Recently,
systematic study on the radiolysis of n-parans has been reported [111113]. The formation
process of dimers and double bonds is assumed as follows.
RHoR
16
oRH H
2
17
R
1
R
2
! R
1
H R
2
H 18
! R
1
R
2
19
Here R(H) is corresponding to alkenes.
2.3. Radiolysis of HNO
3
Radiolysis of aqueous nitrate solution has been investigated not only from practical view-
points in nuclear technology, but also from scientic interests in order to understand the
radiolysis of water because nitrate ion is an ecient scavenger for hydrated electron [114]
and even for the precursor of the hydrated electron [115]. In practical process, the con-
centration range of nitrate covers frommillimolars to 10 Mand the radiation eect not only
in diluted nitrate solutions but also in concentrated ones should be considered.
Table 2 G-Values of TBP g-Radiolysis Products
Product Burr [94]
Wilkinson and
Williams [95]
Wagner
et al. [96]
Holland
et al. [97]
Burger and
McClanahan [98]
H
2
1.73 1.11 1.59 2.02
CH
4
0.072 0.05 0.07 0.032
C
2
0.18 0.24 0.13
C
3
and C
4
0.66 0.45 0.75
DBP 2.44 1.52 2.25 3.71 1.9
MBP 0.14 0.12 0.39 0.3
Polymer 2.47
Table 3 G-Values of n-Hexadecane g-Radiolysis Products
Product Holland et al. [97] Dewhurst [109]
Rappoport and
Ga uman [110]
H
2
6.71 4.9 4.9
CH
4
0.05 0.05 0.01
Dimer 1.4
In diluted solutions, the reduction of NO
3
with e
aq
and H generates NO
2
radicals
through the transient intermediates of NO
3
2
, HNO
3
, and H
2
NO
3
which are in equi-
librium with one another. The reactivity of H atoms towards NO
3
is much lower than e

aq
.
NO
3
e
aq
! NO
2
3
k 9:7 10
9
M
1
sec
1
114 20
NO
3
H ! HNO
3
k 1:0 10
7
M
1
sec
1
114 21
NO
2
3
ZHNO
3
ZH
2
NO
3
pK
1
4:8; pK
2
7:5 114 22
NO
2
3
H
2
O ! NO
2
2OH
k 1:0 10
3
M
1
sec
1
116;117 23
HNO
3
! NO
2
OH
k 2:0 10
5
M
1
sec
1
116;117 24
H
2
NO
3
! NO
2
H
2
O k 7:0 10
5
M
1
sec
1
116;117 25
The NO
2
radicals tend to recombine with each other and, as a result, N
2
O
4
appears. The
N
2
O
4
decays slowly into HNO
2
and HNO
3
through hydrolysis reaction.
NO
2
NO
2
ZN
2
O
4
k
forward
4:5 10
8
M
1
sec
1
118 26
k
backward
6:0 10
3
M
1
sec
1
118
N
2
O
4
H
2
O ! HNO
2
HNO
3
k 18M
1
sec
1
118 27
In the radiolysis of nitric acid, HNO
2
and H
2
O
2
are formed. They strongly aect the solvent
degradation, oxidation states of metal ions, and corrosion condition of the material.
However, HNO
2
and H
2
O
2
are not coexisting because the next reaction will take place.
HNO
2
H
2
O
2
! HNO
3
H
2
O 28
This reaction is composed of several steps as follows [119,120].
HNO
2
H
ZH
2
NO
2
29
H
2
NO
2
H
2
O
2
! HOONO H
2
O 30
HOONO ! NO
3
H
k 4:6 10
3
H
M
1
sec
1
31
In concentrated solutions, direct action of nitrate ion is also taken into consideration.
In addition, in concentrated nitric acid, nitric acid molecule (HNO
3
) coexists. Although it is
known that NO
3
plays an important role in concentrated nitric acid, precise formation
process was not known. Recently, it was claried that the formation of the NO
3
radical is
formed by two dierent processes: reaction of OHwith molecular HNO
3
and direct action of
radiation to HNO
3
and NO
3
[121]. Experimentally obtained temporal behavior of NO

3
and its yield as a function of nitrate ions are shown in Figs. 7 and 8, respectively.
OH HNO
3
! NO
3
H
2
O k 1:4 10
8
M
1
sec
1
32
Therefore the NO
3
radical is not formed in diluted nitrate solutions because OH does not
react with NO
3
. This nding suggests that the OH reacts with molecular HNO

3
through H
atom abstraction. The formation of NO
3
through direct process is in proportion to the
electron fraction of nitrate. In nitric acid, NO
3
is formed through two formation processes,
but, in concentrated nitrate solutions, only direct process plays a role. The direct action of
radiation is commonly observed in concentrated solutions and examples are reviewed in Ref.
122.
For the formation of HNO
2
and O
2
, the following reactions due to the direct eect to
the solute have been proposed in aqueous solutions [123], molten salts, and crystals [124],
having the G-values of g
s2
and g V
s2
.
NO
3
oO NO
2
33
g
s2
NO
3
g
s2
NO
2
g
s2
O 34
HNO
3
oO HNO
2
35
g
s2
V HNO
3
g
s2
V HNO
2
g
s2
V O 36
Figure 7 Formation of NO
3
radical observed at 640 nm in 3 M HNO
3
and 6 M NaNO
3
solutions
in the presence and absence of 0.1 M ethanol. (From Ref. 121.)
Figure 8 Dependence of G(NO
3
) as a function of nitrate concentration in HNO
3
and NaNO
3
,
respectively: total (.) and fast formation process (E) yields in HNO
3
solution; fast formation
process yields in LiNO
3
(j) and NaNO
3
(5) solutions. (From Ref. 121.)
The O formed is in a singlet (
1
D) or triplet (
3
P) state. It is known that the O (
1
D) will react
with water to yield H
2
O
2
and this does not contribute to the formation of HNO
2
and O
2
.
Therefore O (
3
P) is needed to explain the formation of O
2
and HNO
2
.
O
1
D H
2
O ! H
2
O
2
37
O
3
P NO
3
! O
2
NO
2
38
The rate constant of the second reaction is estimated to be k[O(
3
P)+NO
3
] =2.210
8
M
1
sec
1
fromthe values of [O(
3
P)+O
2
] =4.010
9
M
1
sec
1
[125] and k[O(
3
P)+NO
3
]/k[O
(
3
P)+O
2
] = 5.610
2
M
1
sec
1
[126]. However, another possible direct path, NO
3
o
O
+NO
2
, does not contribute to the O
2
formation.
The yield of HNO
2
fromwater decomposition, G
W
(HNO
2
), can be calculated by using
the yields of water decomposition products and their material balance relation:
G
W
HNO
2
f
W
0:5g
W
e
aq
H 0:5g
W
OH g
W
H
2
O
2
f
W
g
W
H
2
GH
2
39
Here f
W
stands for the electron fraction of water in the solution. Thus the electron fraction of
the solute is f
S
=1f
W
. In addition, G(HNO
2
), G(H
2
), and G(O
2
) are G-values of HNO
2
, H
2
,
and O
2
formation, respectively, experimentally determined in the solution. Reported G(H
2
)
and G(O
2
) in nitric acid and sodium nitrate solutions are summarized in Fig. 9 [127].
The total yield of HNO
2
in nitric acid, G(HNO
2
), coming from the direct and indirect
eect, G
W
(HNO
2
) and G
S
(HNO
2
), can be expressed as:
GHNO
2
G
W
HNO
2
G
S
HNO
2
GH
2
G
S
HNO
2
40
The values of G(HNO
2
)+G(H
2
) and G(O
2
) could be expressed by using a, the dissociation
constant of molecular nitric acid [128].
GHNO
2
GH
2
2f
S
ag
s2
NO
3
1 ag V
s2
NO
3
41
GO
2
f
S
ag
s2
NO
3
1 ag V
s2
NO
3
42
Figure 9 Reported G(H
2
) and G(O
2
) as a function of nitrate concentration in g-radiolysis of HNO
3
and NaNO
3
solutions. (From Ref. 127.)
From the experimentally determined values of G(HNO
2
), G(H
2
), and G(O
2
), the values of
g
s2
(NO
3
)=1.7 and g V
s2
(NO
3
)=2.2 were obtained [129]. The value of 2G(O

2
) is
expected to be equal to G(HNO
2
); the relation is almost satised, although there are large
experimental errors. From this experiment, the possibility of O (
1
D) formation is not
excluded, but the experimental nding that H
2
O
2
does not increase at higher concentrations
suggests that it is not signicant. The NO
2
and NO
3
radicals including other nitrogen oxides
in radiolysis of nitrate aqueous solutions and G-values of reported H
2
, O
2
, NO
2
, and H
2
O
2
have been reviewed [130].
The H
2
evolution is an important safety assessment in the commercial process and
much work has been conducted [131]. The G(H
2
) is decreasing with increasing of the
concentration of nitric acid. Coexisting ions aect the H
2
evolution slightly. Ions such as
Rh
3+
, Sm
3+
, Pr
3+
, Ce
3+
, Cd
2+
, Ce
4+
, and Eu
3+
increase the H
2
evolution in this order
and, contrarily, the presence of Fe
3+
and Cr
3+
reduces the evolution. At higher temper-
ature, the G(H
2
) is higher. It was also found that H
2
evolution is strongly dependent on the
depth of the liquid of nitric acid solution: deeper liquid gives smaller evolution than a
shallower one [131,132]. The eect was observed in both g- and a-radiolysis, and the eect is
more signicant in g-radiolysis [133]. In Fig. 10 [133136], the reported G(H
2
) and G(O
2
) by
a-radiolysis in nitric acid are summarized, and it is clear that G(H
2
) in a-radiolysis is higher
than that in g-radiolysis in diluted solution, but the dierence is not signicant in
concentrated solutions.
2.4. Radiolysis of the Mixture of TBP, n-Hexadecane, and HNO
3
Since, during the actual process, TBP, n-dodecane, and HNO
3
are used in a mixture or
contact condition, the degradation is aected by many factors: composition, concentration
of nitric acid, concomitant metal ions, and irradiation conditions such as aerated or
deaerated, stirring or settling, and high or low dose rate. As a result, a variety of products
are formed as summarized in Fig. 11 [137]. Under aerated condition, organic radicals react
with O
2
quickly to form peroxy-radical and after successive reactions bring variety of
alcohols, ketones, peroxides, and carbonyl compounds. These products are roughly
classied into nitration and oxidation products. The ratio of the nitration products to
oxidation product, g=(nitration/oxidation), is 0.8 under sucient oxygen supply but is
increasing to 8 under insucient oxygen. Recent advancement of the analytical technique
brings more precise data [138].
2.5. Radiation Chemistry of Actinide Ions
Because of the multivalent nature of the actinide ions, understanding the radiation-induced
change of the valence-state of the actinide in solutions under self-irradiation or external
irradiation is a challenge in radiation chemistry. Some of the ions are strong a-emitters. It is
also important from a practical viewpoint that the solution chemistry of actinide ions is
closely related to the storage and the repository of the wastes. Much work combined with
experiment and simulation has been conducted and reviews were summarized [136,140
144].
2.6. Storage of Radioactive Waste
In 50 years of production of electrical power and weapons fromthe nuclear fuel, the United
States has accumulated millions of cubic meters and tens of billions curies of radioactive
Figure 10 Reported (a) G(H
2
) and (b) G(O
2
) as a function of nitrate concentration in a-radiolysis
of HNO
3
solution. In (a), from Ref. 134 (E) and Ref. 133 (5: 9.3 g/L, w : 13 g/L, D: 18.5 g/L, .: 30 g/
L, n: 37 g/L, o: 100 g/L, and x: 160 g/L). In (b), from Ref. 134 (o), Ref. 135 (E), and Ref. 133 (D:
210 g/L, w : 160 g/L, and .: 100 g/L). (From Ref. 133.)
wastes [145]. It is widely recognized that safe treatment and storage of these wastes is an
urgent problem to be solved. At a radioactive waste storage tank, the so-called SY-101 in
Hanford, an intermittent gas evolution was found in 1980s. The released gas, composed of
H
2
, N
2
O, and minor NH
3
, in addition to air was emitted every 813 weeks. The content of
the tank is a mixture of chirate agents and their fragments, carboxylic acids, and alkanes in
addition to the sodiumnitrate and nitrite salts, which were produced during the processes to
separate plutonium from uranium and the FPs in spent metallic uranium fuel. This gas
evolution was considered to be a very important issue to keep safe storage of the waste, and
much radiolysis study was conducted to understand the mechanism of the gas evolution.
Through the work, subjects on (1) direct eect in concentrated solutions, (2) redox reactions
of NO
x
compounds, (3) radiation degradation of chilators, and (4) reactions in grout,
precipitation, and slurry have been pointed out as key issues for understanding. Details have
been reported elsewhere [146148].
3. RADIATION EFFECTS RELEVANT TO RADIOACTIVE HIGH-LEVEL
WASTE REPOSITORY
3.1. Once Through, Reprocessing, and High-Level Waste Repository
After the operation of the nuclear power stations for a certain period, the spent nuclear
fuel is produced. The spent fuel is reprocessed, and both U and Pu are recovered. At the
Figure 11 Radiolysis products in Purex solvents (TBP, n-dodecane or kerosene, and HNO
3
).
(From Ref. 137.)
same time, radioactive high-level liquid waste (HLLW) composed of ssion products and
trace amount of actinide compounds is also formed. HLLW emits strong radiation in-
cluding g-rays, high-energy electrons, a-particles, and fast neurons. Most of the ssion
products have a half-life less than 1000 years, and activity is dropped 3 orders magnitude
after 1000 years but still the activity remains due to the
99
Tc,
93
Zr, and actinide nuclei with
long lifetimes of million years. Therefore isolation of HLW from the activities and envi-
ronment of human being is the most essential requirement in HLW repository. Many
possible methods have been discussed such as disposal into the outer space from the solar
system, into the deep sea, under the ice in polar area, and so on. Actually, a disposal to
deep underground, geological deposition, has been selected as a reasonable and practical
one. In fact, at rst, the high-level liquid wastes are solidied with silicate glass into a
metal container called canister and are packed into metal container called an overpack
made of thick copper, stainless steel, or carbon steel, which depends on the choice. The
assembly would be placed in the bentonite clay mantle, which is built in the tunnel with
the depth up to more than 1000 m from the surface. Solidication, overpack, and ben-
tonite clay act as the multiple barriers which will prevent the invasion of groundwater to
the overpack and reduce the migration of radioactive and hazardous nuclei to biosphere.
Another option is that the spent fuel is directly contained without reprocessing into an
overpack for disposal, which is called once through. The same geological disposal method
will be applied. The precise procedures of the depository have been summarized in
textbooks [92,93].
In order to assess the integrity of the system, we should know what kind of reactions
would take place when the groundwater invades and the overpack is corroded. Conse-
quently, the solidied waste or spent fuel itself will be in contact with groundwater. Since the
waste would still be seriously activated, radiolysis of groundwater will take place and change
the chemical condition, which might aect the dissolution of the solidied waste or UO
2
of
the spent fuel.
3.2. Carbonate Solution
It is known that (bi)carbonate ions are predominant anions in groundwater with a
concentration as high as 50 mM. Therefore it is necessary to know the radiolysis eects
on groundwater by ionizing radiation from the HLW. A computer set of reaction steps and
reliable kinetic data for the radiolysis of (bi)carbonate solutions at ionic strength close to
groundwater is essential for the overall safety evaluation of geological disposal. The re-
actions of water decomposition products toward (bi)carbonate ions have been investigated
and rate constants have been accumulated. However, a little experimental evaluation of the
formation yield for the products such as formate, oxalate, H
2
O
2
, and so on has been
reported [149152]. Two sets of the reaction mechanismin carbonate solution were reported
[152,153]. In Table 4, recent list is summarized [152].
Here it should be mentioned that the chemical structure of carbonate radical is still
under debate. The reaction of the carbonate radical has been intensively investigated by
pulse radiolysis [154156] and laser photolysis [157], and the pK
a
of HCO
3
radical was
determined to be 7.6 [158] and 9.6 [157,159,160] from the change of the reactivity as a
function of pH. However, recent studies of Raman spectroscopy [160] and pulse radiolysis
[161] of carbonate solution proposed that the carbonate radical is a strong acid and keeps a
chemical form of CO
3
even at below pH 0. Furthermore, dimer formation mechanism has

also been proposed [78].
3.3. Oxychloride and Saline Solution
Seawater is invaded into the groundwater and thus groundwater sometimes contains sodium
chloride, which is called the seawater-type one. One of the possible sites for the repository is
a salt mine. It is assumed that the site does not receive water invasion for so long, and this
indicates the stability of the site. If groundwater invade the site, saline solution would be
irradiated. Thus understanding of the radiolysis of water containing NaCl is also taken into
consideration after the corrosion of the overpack of the HLW. Chloride ion is one species
Table 4 Rate Constants of Radiation-Induced Reactions in Sodium
(Bi)carbonate Aqueous Solution
Reactions
Rate constants
(M
1
sec
1
)
Reactions of CO
2
, HCO
3
, and CO
3
2
(1) H
+
+CO
3
2
=HCO
3
b 5E10
a
(2) CO
2
+H
2
O=H
+
+HCO
3
b 2E4
(3) H
+
+HCO
3
=CO
2
+H
2
O b 5E10
(4) HCO
3
=H
+
+CO
3
2
b 2
(5) CO
2
+e
aq
=CO
2
b 7.7E9
(6) HCO
3
OH CO
3
+H
2
O b 8.5E6
(7) CO
3
2
+
OH CO
3
+OH
b 3.9E8
(8) HCO
3
+H H
2
CO
3
b 4.4E4
(9) CO
3
2
+e
aq
=CO
2
+2OH
H
2
O b 3.9E5
Reactions of CO
3
(10) CO
3
+CO
3
=C
2
O
6
2
b 1.4E7
(11) CO
3
+H
2
O
2
=CO
3
2
+O
2
+2H
+
b 9.8E5
(12) CO
3
+HO
2
=CO
3
2
+O
2
+H
+
b 1E7
(13) CO
3
O
2
=CO
3
2
+O
2
b 4E8
(14) CO
3
CO
=CO
3
2
+CO
2
b (3F1)E8
Reactions of CO
2
(15) CO
2
+e
aq
=HCOO
+OH
H
2
O b 1E9
(16) CO
2
CO
2
=C
2
O
4
2
b 6.5E8
(17) CO
2
+O
2
=CO
2
+O
2
b 2E9
(18) CO
2
+H
2
O
2
=CO
2
+OH
OH b 7.3E5
(19) CO
2
+HCO
3
=HCOO
+CO
3
b (1.0F0.1)E3
Reactions of C
2
O
6
2
and C
2
O
4
2
(20) C
2
O
6
2
=C
2
O
4
2
+O
2
b 1
b
(21) C
2
O
6
2
=HO
2
+OH
+2CO
2
H
2
O b 200F50
b
(22) CO
3
+C
2
O
4
2
=C
2
O
4
+CO
3
2
b (3F1)E3
(23) C
2
O
4
2
+e
aq
=C
2
O
3
4
b 3.1E7
(24) C
2
O
4
2
+
OH C
2
O
4
+OH
b 7.7E6
Reactions of HCOO
(25) CO
3
+HCOO
=HCO
3
+CO
2
b (1.5F0.5)E5
(26) HCOO
OH H
2
O CO
2
b 3.2E9
(27) HCOO
+H=H
2
+CO
2
b 2.1E8
(28) HCOO
+e
aq
=H
2
+CO
2
H
+
b 8E3
a
Read as 5 10
10
.
b
There are relative rate constants. They mean 0.5% of C
2
O
6
2
decomposes via
reaction (20) and 99.5% of C
2
O
6
2
via reaction (21).
Source: Ref. 152.
among oxychlorides and redox reactions induce conversion from one species to another,
which complicates. Recently, it is recognized that oxychlorides play important roles in
atmospheric and environmental chemistry. Oxychlorides are widely used to breach and to
sterilize water. Some oxychlorides exhibit chemical oscillation which is discussed from
viewpoints of chaos and complex system. Much knowledge has been accumulated. While the
reliable reaction sets of oxychloride in aqueous solution are not fully established, a typical
example of the literature survey is shown in Table 5 [162185].
Table 5 Rate Constants of Radiation-Induced Reactions in Aqueous Oxychloride Solution
Reactions Rate constants (M
1
sec
1
) Reference
(1) Cl
+OH!ClOH
4.3E9
a
[162]
(2) ClOH
!OH+Cl
6.1E9 sec
1
[162]
(3) ClOH
+H
+
!
Cl+H
2
O 2.1E10 [162]
(4)

Cl+H
2
O!ClOH
+H
+
1.6E5 sec
1
[163]
(5)

Cl+OH
!ClOH
1.8E10 [163]
(6)

Cl+OH!HClO 1E9 Assumed
(7)

Cl+Cl!Cl
2
8.8E7 [164]
(8)

Cl+Cl
!Cl
2
2.1E10 [162]
(9) Cl
2
Cl+Cl
1.1E5 sec
1
[162]
(10)

Cl+Cl
ZCl
2
K=1.9E5, 4.7E3 M
1
[162,165]
(11) ClOH
*
!
Cl+OH
23 sec
1
[163]
(12) ClOH
+Cl
!Cl
2
+OH
9E4 [166]
(13) Cl
2
+OH
!ClOH
+Cl
4.5E7 [167]
(14) Cl
2
H!2Cl
+H
+
8E9, (7E9) [168,169]
(15) Cl
2
OH!HClO+Cl
1E9 [170]
(16) Cl
2
+H
2
O!
OH+H
+
+2Cl
7.2E3, 1.3 E3 sec

1
[170]
(17) OH+H
+
+2Cl
!Cl
2
+H
2
O 2.11E11 M
3
sec
1
[170]
(18) Cl
2
+H
2
O
2
!HO
2
+2Cl
+H
+
1.4E5 [167]
(19) Cl
2
+HO
2
!2Cl
+H
+
+O
2
1.0E9 [169]
(20) Cl
2
+Cl
2
!Cl
3
+Cl
4.0E9 [169] (2k)

(21) Cl
2
Cl!Cl
3
6.3E8 [164]
(22) Cl
2
+HO
2
!Cl
2
+H
+
+O
2
1.0E9 [171]
(23) Cl
2
+Cl
!Cl
3
1.8E5 [172]
(24) Cl
2
+H
2
O!HClO+H
+
+Cl
11 sec
1
[173]
(25) HClO+H
+
+Cl
!Cl
2
+H
2
O 1.8E4 M
2
sec
1
[173]
(26) Cl
2
+OH
!HClO+Cl
3.8E11 [153]
(27) Cl
2
+2ClO
2
!2ClO
2
+2Cl
2.1E1 [Cl
2
(aq)] [ClO
2
] [174]
(28) HClO+2ClO
2
+H
+
!2ClO
2
+Cl
+H
2
O 1.06E6 [HOCl] [ClO
2
] [H
+
] [174]
(29) 2HClO+ClO
2
!ClO
3
+Cl
2
+H
2
O 2.1 E3 M
2
sec
1
[175]
(30) HClO+
Cl!Cl
+ClO
+H
+
3E9 [163]
(31) HClO+H
2
O
2
!H
2
O+O
2
+H
+
+Cl
3.4E3 Assumed
(32) Cl
2
+H
2
O!Cl
2
OH
+H
+
6.12E2 sec
1
[173]
(33) Cl
2
OH
+H
+
Cl
2
+H
2
O 2E10 [173]
(34) Cl
2
OH
+H
+
!Cl
2
+OH
+H
+
2E5 [173]
(35) Cl
2
+OH
+H
+
!Cl
2
OH
+H
+
1E10 [173]
(36) Cl
3
!Cl
2
+Cl
1.6E6 [172]
(37) Cl
3
H!Cl
+Cl
2
+H
+
3E10 [176]
(38) Cl
3
+HO
2
!Cl
2
+Cl
+H
+
+O
2
1.0E9 [171]
(39) HClO+e
aq
!Cl
OH 6.5E8 [177]
(40) ClO
+e
aq
!Cl
+O
5.3E10, 8.3E9, 7.0E9 [168,177,178]

(41) HClO+
H!HCl+OH 3E9 Assumed

(42) HClO+
OH!Cl
+H
2
O 1.4E8 [177]
In repository of HLW in salt mine, the understanding of radiolysis of concentrated
NaCl up to 5 M is important. In addition, a-radiolysis by actinide ions dissolved is also
taken into account. There are several reports mentioned above [186192].
3.4. Radiation-Induced Dissolution of UO
2
Fuel
In direct geological depository of the spent fuel, dissolution of UO
2
matrix into groundwater
plays a key role for the release of the radionuclides to the biosphere. Therefore mechanismof
Reactions Rate constants (M
1
sec
1
) Reference
(43) ClO
OH!ClO
+OH
9.0E9, 2.7E9 [168,177]

(44) ClO
+O
(+H
2
O)!ClO
+2OH
2.4E8 [168]
(45) ClO
Cl!ClO+Cl
8.2E9 [163]
(46) ClO
+O
2
!O
+O
2
+Cl
7.7E6 [179]
(47) ClO
+H
2
O
2
!H
2
O+Cl
+O
2
3.4E3 [180]
(48) ClO
+HO
2
!OH
+Cl
+O
2
4.4E7 [181]
(49) HClO!ClO
+H
+
3.0E2 pKa=7.53
(50) ClO
+H
+
!HClO 1E10 [181]
(51) HClO+ClO
2
+H
+
!Cl
2
O
2
+H
2
O 1.12E6 M
2
sec
1
[175]
(52) Cl
2
O
2
+ClO
2
!2ClO
2
+Cl
5.4E4(
f
1E5) [175]
(53) 2Cl
2
O
2
!2ClO
2
+Cl
2
6E10 M
1
sec
1
[175]
(54) ClO
2
+Cl
2
!Cl
2
O
2
+Cl
4.010
4
[175]
(55) Cl
2
O
2
+H
2
O!ClO
3
+Cl
+2H
+
1, 10 sec
1
[175]
(56) ClO
+ClO
+H
2
O!ClO
+ClO
2
+2H
+
2.5E9 [163]
(57) ClO
+ClO
2
!ClO
+ClO
2
9.4E8 [182]
(58) ClO
2
+e
aq
!ClO
+O
4.5E10, 4.0E9, 2.5E9 [168,177,183]

(59) ClO
2
OH!ClO
2
+OH
6.3E9, 7.9E9, 7E9 [168,177,183]

(60) ClO
2
+O
(+H
2
O)!ClO
2
+2OH
2.0E8, 1.9E8 [168,183]

(61) H
+
+ClO
2
!HClO
2
1.0E10 pKa=2.5
(62) HClO
2
!H
+
+ClO
2
3.16E7 sec
1
[174]
(63) ClO
2
+HO
2
!ClO
2
+HO
2
8E4, 1.3E5 [183,184]
(64) ClO
2
+O
2
!ClO
2
+O
2
3.3E9 [183]
(65) ClO
2
+ClO
!Cl
2
O3 1E9 Assumed
(66) Cl
2
O3+H
2
O!ClO
+ClO
3
+2H
+
1E4 Assumed
(67) ClO
2
+
OH!overall 3.5E9, 4.0E9 [177,185]

(68) ClO
2
+
OH!HClO+O
2
1.4E9 [185]
(69) ClO
2
+
OH!ClO
3
+H
+
2.6E9 [185]
(70) ClO
2
+O
!overall 2.7E9 [185]

(71) ClO
2
+O
!ClO
+O
2
4.9E8 [185]
(72) ClO
2
+O
!ClO
3
2.2E9 [185]
(73) ClO
2
+e
aq
!overall kq=2.1E10 [177]

(74) ClO
2
+
e
aq
!ClO
2
qkq **
(75) ClO
2
+
e
aq
!ClO
(1q)kq **
(76) ClO
2
+
H!overall ks=110
9
Assumed
(77) ClO
2
+
H!H
+
+ClO
2
sks **
(78) ClO
2
+
H!ClO
OH (1s)ks **
*The dissociation rate is calculated after the assumption of the recombination rate constant of H
+
with anion to
be 10
10
M
1
sec
1
when the pK
a
value is known.
**Branching reaction. q (s) and 1q (1s) are the branching fraction.
a
Read as 4.3 10
9
.
Table 5 Continued
the dissolution processes has been claried by using irradiated and unirradiated UO
2
under
various conditions. Inuence of many factors such as radiolysis, pH, temperature, ground-
water composition, and formation of corrosion deposits has been investigated. An excellent
review has been published elsewhere [193]. Among many factors, it was revealed that
radiolysis accelerates the dissolution of UO
2
.
The accelerated dissolution of UO
2
and U
2
O
8
in acid or carbonate solutions under the
irradiation of g-rays was found by Gromov in 1981 [194]. Since then, much experimental
results have been accumulated as summarized in a review of Cristensen and Sunder [195].
The radiolysis products such as OH and H
2
O
2
react with UO
2
, and its surface is oxidized to
form higher oxidizing phase: UO
2+x
, UO
2.33
, UO
2
2+
, and so on. The measurement of the
corrosion potential of the specimen was also done and showed the correlated behavior of the
oxidizing process. There is a time-dependent generation of oxidants and reductants at fuel/
water interface due to a-, h-, and g-radiolysis. Based on the accumulated experimental data,
a calculation code to predict the oxidation and dissolution process was proposed and the
calculated results are in good agreement with the experimental ones [195].
Nuclear spent fuel UO
x
emits not only gamma and beta, but also alpha particles. The
alpha activity lasts over a million years, much longer than the gamma and beta activities
which decay within a few hundred years. In long-term assessment, a-radiolysis should be
also taken into consideration. Recently, a model experiment using He
2+
ion beam from an
accelerator has been investigated and a signicant acceleration of dissolution under beam
irradiation was found, and the formation of uranium peroxide hydrate UO
4
2H
2
O (meta-
studtite) was detected from x-ray diraction at UO
2
surface [196,197].
4. CONCLUSION
It is clear that the development of nuclear technology is impossible without the support of
radiation chemistry. Thus the radiation chemistry is important not only in basic science, but
also in technology.
ACKNOWLEDGMENT
This is supported by the Japan Society for the Promotion of Science under the contract
JSPS-RFTE 98P00901. This is also partly supported by the innovative basic research
program in the eld of high-temperature engineering using HTTR conducted by Japan
Atomic Energy Research Institute.
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24
Electron Beam Applications to Flue
Gas Treatment
Hideki Namba
Japan Atomic Energy Research Institute, Takasaki, Gunma, Japan
1. INTRODUCTION
The emission of toxic gases, sulfur oxides (SO
x
), and nitric oxides (NO
x
) from industrial
plants has become a serious problem in many countries. Fig. 1 shows the sources of SO
x
and
NO
x
emission, which are recognized as the origin of dry and wet deposition known as acid
rain [1].
These toxic components sometimes travel more than a thousand kilometers and cause
problems in other places and, in some cases, in other countries. Therefore the problem of air
pollution attracts worldwide attention. Among these, the coal-red ue gas from thermal
power plants has been recognized as one of the main sources of environmental pollution,
because of its larger amount of S and N components. Now many countries are introducing
stricter emission control regulations to solve the problem.
Fig. 1 also shows the chemical reaction mechanism of SO
x
and NO
x
in air for
producing acid rain [2]. The radicals (O, OH, and HO
2
) produced in air play an important
role in oxidizing SO
x
and NO
x
to produce sulfuric acid and nitric acid, which are the main
components of acid rain. Some of these reactions also occur in a reaction chamber of
electron beam treatment of ue gas.
Electron beam treatment of ue gas was rst performed in Japan [3,4] and is now
regarded as a promising pollution control method with many advantages [5,6]: simultaneous
reduction of SO
x
and NO
x
, being a dry process, yields a by-product which can be used as an
agricultural fertilizer, and so on. Fig. 2 shows a ow diagram of electron beam treatment
process for ue gas treatment. In this method, combustion ue gas containing NO
x
(main
component is NO) and SO
x
(main component is SO
2
) is introduced in a spray cooler to
decrease the temperature. After adding ammonia, the ue gas is irradiated with electron
beam in a process vessel. NO and SO
2
are converted to nitric acid and sulfuric acid and are
nally changed to ammonium nitrate and ammonium sulfate which may be used as
agricultural fertilizers. Cleaned ue gas is emitted from a stack. Radiation chemical
reactions induced by electron beam irradiation and related chemical processes will be
studied in detail in this chapter.
2. INCIDENT ELECTRONS
2.1. ElectronNuclei and ElectronElectron Interactions
Accelerated, or energized, electrons by an accelerator are used in ue gas treatment. The
energy of incident electrons for practical treatment process is usually between 300 and 800
kV. The reason for using this energy region will be discussed in Sec. 2.4. The main energy loss
processes of electrons in the region while passing through matter are (1) the interaction with
nuclei to emit x-ray, so-called bremsstrahlung; and (2) the interaction with electrons of the
materials. The contribution ratio of (1) and (2) is dierent depending on the atomic number
Figure 1 Origin of acid rain and chemical reactions in air. (From Refs. 1 and 2.)
Figure 2 Flow diagram of electron beam treatment process for ue gas treatment.
(Z) of materials. At nearly 1 MeV of incident energy, the ratio is EZ/800, where E is the
energy represented in MeV unit. As ue-gas components consist of light atoms, as shown in
Tables 1 and 2, the contribution of (1) is negligible. That means almost all the energy loss of
incident electrons is through inelastic collisions to generate ionization and excitation.
2.2. Stopping Power
In this condition, Bethe formulated the stopping power for electron according to the Born
approximation. Stopping power is a property of irradiated materials and gives the amount
of energy deposited per unit path length, dE/dx.
dE
dx

2pe
4
m
0
v
2
NZ ln
m
0
v
2
E
2I
2
1 b
2

2
1 b
2
q
1 b
2

ln2 1 b
2
1
8
1
1 b
2
q

2
( )
1
Where, E is the energy, x is the length, m
0
and e are the rest mass and charge of
electrons, respectively, v is the velocity of electron, N and Z are the number of atoms in unit
volume and atomic number of the irradiated material, respectively, and b is the relative
velocity represented by v/c, where c is the velocity of light.
In this equation, I is the mean ionization potential, which corresponds to the average
energy used to ionize all the electrons in the atom, and is obtained experimentally. The
values of mean ionization potential for elements in ue gas are listed in Table 1. The ratio of
I=Zdecreases with increasing Z and becomes almost constant for substances with Z greater
than sulfur to be 10 F 1.
For low energy electron region, namely, below 200 Z
2
eV, this equation will not be
valid because of the limitation of Born approximation; in this energy region, the calculations
will be made using electron-impact ionization and excitation cross sections for gaseous
targets [7].
To get more accurate stopping powers, two corrections are added to the basic stopping
power formula. One is shell correction and the other is density eect correction. Including
these eects, the formula will be written as follows [8,9]:
dE
dx

2pe
4
m
0
v
2
NZ ln
m
0
v
2
E
2I
2
1 b
2

1 b
2
q
1 b
2
ln2 1 b
2
1
8
1
1 b
2
q

2
2
C
Z
d
( )
2
Table 1 Mean Ionization Potentials for Elemental Substances
Composing Flue Gas
Z Element I/eV DI/eV (I/Z)/eV
1 H (gas) 19.2 0.4 19.2
6 C (graphite) 78.0 7 13.0
7 N (gas) 82.0 2 11.7
8 O (gas) 95.0 2 11.9
16 S (solid) (180) 11.3
Source: From Ref. 7.
where C is the total shell correction factor, and d is the density eect correction factor that
can be expressed as
d ln
t
2
x
2
p
I
2
1 b
2
!
1 3
where x
p
= (4pNe
2
Z/m)
1/2
is the so-called plasma frequency.
These corrections, however, are not so signicant in ue gas treatment conditions.
2.3. Range
The range is the distance traveled by an electron from its incident point to the point where it
has lost its energy completely; therefore it can be given by the integration of (dx/dE) over
dE from the initial energy to 0. Fig. 3 shows the relation between range and energy of
electrons in water calculated with continuous slowing-down approximation (csda) [10].
Table 2 Typical Concentration of Components in Coal-Fired
Flue Gas and Their Electron Fraction
Components Concentration
Ratio of total number
of electrons
N
2
72% 0.685
O
2
6% 0.065
H
2
O 10% 0.068
CO
2
12% 0.179
NO 225 ppm 0.0002
SO
2
800 ppm 0.0017
Figure 3 Relation between range and energy of electrons in water calculated with csda. (From
Ref. 7.)
For practical use, it is important to knowthe linear distance in the substances fromthe
incident point, i.e., an accelerator window, to the point at which the energy of electrons has
been exhausted. The denitions of range for theoretical consideration and for practical use
are somewhat dierent, however; the range shown in Fig. 3 gives a good indication for
estimating the distance of electrons traveling in substances, which is called maximum range.
Rough estimation of range is possible for other materials, by simply dividing their density.
For example, the density of air is 0.0013 g/cm
3
at normal pressure and temperature; the
range may be estimated about 770 times larger than in water, while that calculated by csda is
about 860 times in this energy region [11]. As the density of the ue gas is almost the same as
that of air, the range in ue gas will be the same as that in air.
2.4. DepthDose Curve and Energy Loss in Windows
The dose distribution in the materials is given as a depthdose curve. An example of the
curve is illustrated in Fig. 4 obtained with the irradiation of electron from 0.5 to 1.0 MeV
using cellulose triacetate (CTA) lmdosimeter [12]. The existence of the maximumdose is an
important characteristic of the depthdose curve. Irradiation from two opposite sides by
using two accelerators was proposed in order to give better uniformity in water [13]. The
uniform irradiation is also important for ue gas treatment. Better eciency of NO
x
removal was proved with both-side irradiation by using three accelerators for coal-red
ue gas than single-side irradiation at the same dose [14].
Fig. 5 shows a schematic representation of an accelerator and a reaction chamber.
Double windows are usually used to separate the accelerator and the chamber. The primary
window keeps the accelerator in vacuum; therefore the window material must have enough
strength to bear the pressure dierence of more than 1 atm. The secondary windowprevents
the primary windowfromue gas in which acidic chemical components are produced during
Figure 4 Depthdose distribution curves in CTA stack lms with the irradiation of electron.
(From Ref. 11.)
irradiation. That means the windows material might be anticorrosive. In order to minimize
the energy loss in the windows, both windows should be thin. In most cases, the windows are
made of metal or plastic lms with a thickness of a few micrometers to a few tens of mi-
crometers. Titanium or its alloy foils are commonly used for industrial-scale plants. Table 3
shows the power penetration eciency of the windows and air-layer, which are the inverse of
energy loss and beam current loss [15]. At lower energy of incident electrons, the energy loss
is not negligible at the windows region. The eciency increases with increasing energy of
accelerated electron; however, we need a rather large installation to obtain higher energy of
electrons. Thus accelerators with an energy region of 300 to 800 keV are commonly used for
large-scale practical plants.
Figure 5 Schematic representation of accelerator and reaction chamber for ue gas treatment.
Table 3 Power Penetration Eciency of Electron with Dierent Incident
Energy at Windows and Air Layer
Materials Ti (30 Am) Air (5 cm) Ti (17 Am) Total
300 keV 0.56
Energy 0.87 0.945 0.89
Beam 0.86 0.995 0.9
500 keV 0.79
Energy 0.93 0.974 0.95
Beam 0.945 1.0 0.97
300 keV 0.88
Energy 0.96 0.985 0.97
Beam 0.975 1.0 0.98
1 MeV 0.90
Energy 0.97 0.99 0.975
Beam 0.98 1.0 0.98
Source: From Ref. 15.
3. INITIAL PROCESS
3.1. Energy Absorption to Produce Primary Species
The energy, or power, of electron beam induced in the ue gas is divided and absorbed by
their gas components roughly depending on their electron fraction. Therefore almost all
the energy is absorbed by the main components of the ue gas, namely, N
2
, O
2
, CO
2
, and
H
2
O. Table 2 shows a typical concentration of the components in coal-red ue gas in
Japan. The ratio of the total number of electrons in each gas components is also listed in
the same table. The energy absorbed directly by the toxic components (SO
2
and NO) is
negligibly small. For electron beam treatment of ue gas, ammonia gas is added to the
ue gas before the irradiation. The amount of ammonia is usually set as stoichiometrically,
i.e., 2D[SO
2
] + D[NO], where D[SO
2
] and D[NO] are the concentrations of SO
2
and NO
intended to be treated, respectively. The concentration of ammonia is usually higher than
the initial concentration of SO
2
and NO; however, it is still far lower than that of the main
components.
The rst processes produced by high-energy charged particles are ionization and
excitation. Evaluating the amount of energy deposited in molecules is one of the key factors
in radiation chemistry, both theoretically and experimentally. The incident electron pro-
duces other electrons while losing its energy during ionization. The ionized electrons also
produce other electrons till the energy reached is less than ionization potential. These are
called secondary electrons. As the W-value in air is
f
30 eV, a single electron with an
energy of 750 kV will produce 25,000 electrons. That means energy deposition to the mate-
rials is mainly by the secondary electrons.
In order to estimate the contribution of secondary electrons, degradation spectrum,
or in other words slowing down spectrum, is used. Degradation spectrum is dened as the
length of the secondary electron trajectory, where the electron with the initial energy E
o
dissipates its energy between E and E+dE.
Once we can obtain the degradation spectrum and the cross section of each reaction
to produce the initial species, the yields of all the initial species are determined with the
following equation [16];
N
s
N
X
i
n
i
Z
T
max
T
z
yTQ
s
Td T 4
or
N
s
N
X
i
n
i
Z
T
max
T
z
TyTQ
s
Td ln T 5
where N
s
is the number of produced initial species, N is the number density, n
i
is the number
of electron at ith discreet energy level, T is the energy of electron (eV), Q
s
(T) is the cross
section (cm
2
), and y(T) is the degradation spectrum (cm/eV). Fig. 6 shows the electron
degradation spectrum in gaseous nitrogen calculated by binary-encounter collision theory
with an irradiation of 100 keV electron [17]. Examples of contribution of the electron
degradation spectrum to ionization and excitation are also listed in the same gure. The
ionization in the gure shows an ionic process, N
2
oN
2
+
(X
2
Ag
+
) + e
. The hatched area

corresponds to the integral term of Eq. (3) for the process. The diculty, however, is how to
get all the precise cross-section data in order to calculate the accurate amount of energy
separated from the discreet energy levels.
To avoid this problem, Wills and Boyd have applied a semi-empirical method [18].
They used relative cross sections for 100 eV electrons and calculated the yields for the
various processes based on the W-values. This method is rather simple and contains many
assumptions; nevertheless, the results are a good indication for radiation chemists to provide
a specic amount of initial species. The following equations [19] show the amounts of initial
species from the main components of ue gas with electron beam irradiation based on the
data listed in Ref. 18.
4:43N
2
o
2:27N
2
0:69N
2:96e
0:885N
2
D 0:295N
2
P 1:87N
4
S 0:29N
2
*
5:377O
2
o
2:07O
2
1:23O
3:3e
2:25O
1
D 2:8O
3
P 0:18O* 0:077O
2
*
7:33H
2
O
o
1:99H
2
O
0:01H
2
0:57OH
0:67H
0:06O
3:3e
0:46O
3
P
4:25OH4:15H0:51H
2
*
6
7:54CO
2
o
2:24CO
2
0:51CO
0:07C
0:21O
3:03e
5:16O
3
P 4:72CO
where the numerical coecients are the amounts of decomposed molecules or produced
species with 100-eV energy absorption, i.e., the G-values.
Positive ions, electrons, and excited molecules are produced after the irradiation of ue
gas as shown in these equations. These ions and radicals play the most important role in
radiation chemical reactions in ue gas.
Figure 6 Contribution of the electron degradation spectrum to ionization and excitation in gaseous
nitrogen calculated by binary-encounter collision theory with irradiation of 100-keV electron. (From
Ref. 15.)
3.2. Ions and Electrons
As the W-values of the major component of ue gas are nearly 30 eV, the total amount of
positive ions produced will be
f
3 in G-value. The most important reaction of positive ions is
that with H
2
O. For example, N
2
+
reacts with H
2
Oto produce OHradical, decomposing H
2
O
through charge transfer reaction.
N
2
2H
2
O !H
3
O
OHN
2
7
In a real case, part of the positive ion will be produced through more complex pathways,
such as forming N
4
+
, forming ion clusters with H
2
O, and so on. In any case, however, the
nal positive ion will be H
3
O
+
or its clustered ions, H
3
O
+
(H
2
O)
n
. Other positive ions, O
2
+
,
H
2
O
+
, and CO
2
+
, will behave in the same way.
O
2
2H
2
O !H
3
O
OHO
2
H
2
O
2H
2
O !H
3
O
OHH
2
O 8
CO
2
2H
2
O !H
3
O
OHCO
2
On the analogy of these reactions, the radical ions, N
+
, O
+
, and H
+
, will produce
radicals and positive ions in the following events.
N
2H
2
O !H
3
O
OHN
O
2H
2
O !H
3
O
OHO 9
H
2H
2
O !H
3
O
OHH
These positive ions are the main source of the OH radical, which is one of the most
important radicals for electron beam treatment of ue gas as will be discussed in the next
section.
Electrons react mainly with O
2
to produce O
2
or its clustered ion.

e
O
2
M!O
2
M 10
where M is a third body for the reaction.
These positive and negative ions neutralize to form HO
2
.
H
3
O
O
2
!HO
2
H
2
O 11
Therefore one pair of ions produces one OH and one HO
2
radicals. The total amount of
radicals, which are produced in ue gas by electron beam irradiation, is possible to calculate
using reported G-values. The main radicals produced initially through direct and ionic
decomposition processes are OH, N, HO
2
, O, and H.
4. CHEMICAL REACTIONS
4.1. Radical Reactions
The radicals produced by irradiation will react with NO and SO
2
, which are well-known
good radical scavengers. These radical reactions related to NO
x
and SO
x
removals are very
complicated with more than a few hundreds of reaction pathways [20]. The main radical
reactions committed to the removal of NO
x
and SO
2
are summarized in Table 4.
The total amount of radicals produced after irradiation is estimated at
f
10 molecules/
100 eV ( G-value) from Eq. (6) and from discussions in the previous section. The following
equation will help us to compare the amount of radicals with the concentration of NO and
SO
2
that we are going to treat:
C 0:104 M
w
DG 12
where Cis the concentration (ppm), M
w
is the molecular weight (g/mol), Dis the dose (kGy),
and G is G-value (molecules/100 eV). Because M
w
is almost the same as air (29 g/mol) in ue
gas, the concentration will be 300 ppm at G = 10 and D = 10 kGy.
Some radicals produce other radicals through the reactions shown in Table 4.
Comparing the calculated amount of NO and SO
2
removals through radical reactions to
the experimental results [21], it indicates that NO
x
removals mainly occur through radical
reactions, while SO
2
removals mainly occur through other processes, so-called thermal
reactions, or heterogeneous reactions. More details will be given in the following sections.
Table 4 Main Radical Reactions
Related to the Removal of NO
x
and
SO
2
OH+NO+M ! HNO
2
+M
OH+SO
2
+M ! HSO
3
+M
OH+NO
2
+M ! HNO
3
+M
OH+NO
2
! NO+HO
2
OH+HNO
2
! NO
2
+H
2
O
OH+NH
3
! NH
2
+H
2
O
OH+CO ! CO
2
+H
N(
4
S)+NO ! N
2
+O
N(
4
S)+NO
2
! N
2
O+O
N(
2
D)+O
2
! NO+O
N(
2
D)+NH
3
! NH+NH
2
N(
2
P)+O
2
! NO+O
N(
2
P)+NH
3
! NH+NH
2
HO
2
+NO ! NO
2
+OH
HO
2
+SO
2
! SO
3
+OH
O(
1
D)+H
2
O ! 20H
O(
1
D)+M ! O(
3
P)+M
O(
3
[Pub])+O
2
+M ! O
3
+M
O(
3
[Pub])+NO+M ! NO
2
+M
O(
3
[Pub])+NO
2
! NO+O
2
H+O
2
+M ! HO
2
+M
NH
2
+NO ! N
2
+H
2
O
NH
2
+NO
2
! N
2
O+H
2
O
NH+NO ! N
2
+OH
NH+NO
2
! N
2
O+OH
HSO
3
+O
2
! SO
3
+HO
2
O
3
+NO ! NO
2
+O
2
SO
3
+H
2
O ! H
2
SO
4
M is a third body molecule.
4.2. NO
x
Removal
Fig. 7 shows the main reaction pathways to remove NO
x
. NOwill react with Oradical or O
3
,
in which O
3
is produced with the reaction of O
2
.
NOO
3
P M!NO
2
M
O
3
P O
2
M!O
3
M 13
NOO
3
M!NO
2
O
2
M
Another important reaction to oxidize NO is that with HO
2
.
NOHO
2
!NO
2
OH 14
This NO
2
is converted to nitric acid with the reaction of OH and nally changes to
ammonium nitrate with the chemical reaction of ammonia.
NO
2
OHM!HNO
3
M
15
HNO
3
NH
3
!NH
4
NO
3
This oxidization is the main process of NO
x
removal.
Another important pathway for removing NO
x
is reaction of NO with ground-state
nitrogen radical N(
4
S) or NH
2
radical, in which NH
2
radical is produced with the reaction of
NH
3
and OH. Nitrogen molecules are produced with these reactions [22].
NON
4
S !N
2
O
NH
3
OH !NH
2
H
2
O 16
NONH
2
!N
2
H
2
O
With the same type of reaction, dinitrogen monoxide is produced [23].
NO
2
N !N
2
OO
17
NO
2
NH
2
!N
2
OH
2
O
Nitrous acid is also produced [24] with the reaction of NO and OH; however, this acid
will be oxidized to NO
2
or HNO
3
nally.
NOOHM!HNO
2
M 18
Figure 7 Main reaction pathways for removing NO
x
. Solid line: radical reaction. Dotted line:
thermal reaction.
The ground-state nitrogen radical N(
4
S) decreases NO with reducing reaction;
however, excited-state nitrogen radicals, N(
2
D) and N(
2
P), behave perfectly in another
way to produce NO.
N
2
D;
2
P O
2
!NOO 19
4.3. SO
2
Removal
The main reaction pathways for SO
2
removal are illustrated in Fig. 8. The most important
radical reaction for removing SO
2
is the following reaction to produce HSO
3
.
SO
2
OHM!HSO
3
M 20
This HSO
3
will react with oxygen to form SO
3
and easily react with water to form
sulfuric acid.
HSO
3
O
2
!SO
3
HO
2
21
SO
3
H
2
O !H
2
SO
4
The acid will react with ammonia and become ammonium sulfate.
H
2
SO
4
2NH
3
!NH
4
2
SO
4
22
Sulfur dioxide may react with HO
2
to form SO
3
; however, the reaction (Eq. (14)) will
be overcome when NO simultaneously exists.
SO
2
HO
2
!SO
3
OH 23
In addition to this SO
x
removal process with OH radicals, there exists a so-called
thermal reaction in which SO
2
reacts with NH
3
[2527]. This reaction depends on the
concentrations of NH
3
, SO
2
, and H
2
O, and it has a very large temperature dependence.
5. INDUSTRIAL-SCALE PLANTS AND OTHER FLUE GAS
Large-scale pilot plants have been installed in Indianapolis, USA, in 1984 [28], in Karlsruhe,
Germany, in 1985 [29], in Warsaw, Poland, in 1990 [30], and in Nagoya, Japan, in 1991 [14]
for the treatment of coal-red ue gas with a ow rate of more than 10,000 m
3
/hr at normal
Figure 8 Main reaction pathways for removing SO
2
. Solid line: radical reaction. Dotted line:
thermal reaction.
temperature and pressure. With the success of these pilot-scale tests demonstrating the
feasibility of the process, two large industrial-scale plants were installed in Chengdu, China,
in 1997 and in Pomorzany, Poland, in 2000. The plant in Chengdu is equipped with two
accelerators with a total capacity of 640 kW for treating 300,000 m
3
/hr of ue gas with 1800
ppm SO
2
and 400 ppm NO
x
. The plant is now successfully operating with 80% removal of
SO
2
[31]. The plant in Pomorzany [32] has four accelerators with a total maximum power of
1200 kW to treat 270,000 m
3
/hr of ue gas and has started operation.
The technology for treating ue gas from oil burning boilers is essentially the same as
that from coal-red boilers, because of the same components to treat, i.e., NO
x
and SO
x
.
Containing high concentration of sulfur, heavy oil is regarded as an urgent target; therefore
intensive investigations are going on in many countries. Among them, an industrial-scale
plant for ue gas of 620,000 m
3
/hr will start operation in Nagoya, Japan, in 2003 [33].
The ue gas frommunicipal waste incinerator boilers contains SO
2
, NO
x
, and HCl. To
remove these harmful components simultaneously by dry process, electron beam treatment
method was investigated. The pilot-scale test was conducted in Matsudo, Japan, in 1992
with a ue gas of 1000 m
3
/hr [34]. Recently, dioxins, namely, poly-chlorinated-di-benzo-
paradioxins (PCDDs) and poly-chrorinated-di-benzo-furan (PCDFs), from incinerators
have become a very serious problem because of their high toxicity. Pilot-scale tests to
decompose dioxins by electron beam irradiation were conducted in Karlsruhe, Germany
[35], and in Takahama, Japan [36], using almost the same capacity of ue gas, 1000 m
3
/hr.
Very promising results were obtained with decomposing more than 90% of dioxins.
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Kawamura, K.; Aoki, S.; Adachi, K. Radiat. Phys. Chem. 1977, 9, 371.
5. Electron beam processing of combustion ue gases, IAEA-TECDOC-428, 1987.
6. Environmental Applications of Ionizing Radiation; Cooper, W.J., Curry, R.D., OShea,
K.E., Eds.; John Wiley and Sons, Inc.: New York, 1998.
7. Watanabe, T.; Shimamura, I.; Karashima, S. In CRC Handbook of Radiation Chemistry;
Takahashi, T., Tabata, Y., Itoh, Y., Tagawa, S., Eds.; CRC Press: Boca Raton, 1991; 31 pp.
8. Chatterjee, A. Radiation ChemistryPrinciples and Applications; Farhatazis, Rodgers, M.A.J.,
Eds.; VCH Publishers, Inc.: New York, 1987.
10. Watanabe, T.; Shimamura, I.; Karashima, S.; Takahashi, T. In CRCHandbook of Radiation
Chemistry; Tabata, Y. Itoh, Y., Tagawa, S., Eds.; CRC Press: Boca Raton, 1991; 47 pp.
11. Stopping powers for Electrons and Positrons, ICRU Report 37, International Commission
on Radiation Units and Measurements, Bethesda, 1984.
12. Kanazawa, T.; Haruyama, Y.; Ueno, S.; Yotsumoto, K.; Tanaka, R.; Washino, M.; Yoshida,
K. JAERI-M 86-005, 1986.
13. Woods, J.; Pikaev, K. Applied Radiation Chemistry: Radiation Processing; Wiley-Interscience:
New York, 1994.
14. Namba, H.; Tokunaga, O.; Hashimoto, S.; Tanaka, T.; Ogura, Y.; Doi, Y.; Aoki, S.; Izutsu,
M. Radiat. Phys. Chem. 1995, 46, 1103.
15. Sakamoto, I.; Mizusawa, K.; Kashiwagi, M. In Electron beam processing of combustion ue
gases; IAEA-TECDOC-428, 201, 1987.
16. Rau, A.R.P.; Inokuti, M.; Douthat, D.A. Phys. Rev. 1978, A18, 971.
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Inc., 1991; 315 pp.
20. Ma tzing, H. In Adv. Chem. Phys., LXXX; Prigogine, I. Rice, S.A., Eds.; John Wiley and Sons
Inc., 1991; 360 pp.
21. Namba, H.; Tokunaga, O.; Tanaka, T.; Ogura, Y.; Aoki, S.; Suzuki, S. Proceedings of the
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IAEA-TECDOC-428, 13, 1987.
26. Paur, H.-R.; Jordan, S. Radiat. Phys. Chem. 1988, 31, 9.
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25
Ion-Beam Therapy: Rationale, Achievements,
and Expectations
Andre Wambersie and John Gueulette
Universite Catholique de Louvain, Brussels, Belgium
Dan T. L. Jones
iThemba Laboratory for Accelerator Based Sciences, Somerset West, South Africa
Reinhard Gahbauer
Ohio State University, Columbus, Ohio, U.S.A.
ABSTRACT
Radiation therapy is a very important and eective treatment modality for almost all types
of malignancies. Its importance in the local control of primary or bulky cancers will even
increase in the future if more eective chemotherapeutic or other systemic treatments
become available to treat metastatic disease.
Improvements in the physical selectivity, from orthovoltage x-ray to cobalt-60 and
high-energy linear accelerators, combined with more powerful diagnostic tools and radia-
tion delivery methods have continuously improved the results of photon therapy (3-D or
inverse planning, conformal- and intensity-modulated radiation therapy, and stereotactic
methods). The safety and the reliability of photon therapy are well established.
However, newtypes of radiation continue to be explored with the aimof improving the
physical selectivity, the radiobiological dierential eect, or both. In this context, the role of
fast neutrons with their biological selectivity in selected cancer sites and of protons with their
superb physical selectivity will be reviewed.
Fast neutrons were the rst nonconventional radiation used in cancer therapy. Fast
neutrons (a high-LET radiation) were introduced for the following radiobiological reasons:
(1) a reduction of the OER with increasing LET; (2) a reduction in the dierence in
radiosensitivity related to the position of the cells in the mitotic cycle; (3) and less repair and
thus less clinical relevance of the dierent repair mechanisms. The best and clinically proven
indications for fast neutrons are salivary gland tumors, locally advanced prostatic adeno-
carcinomas, and slowly growing, well-dierentiated sarcomas.
Radiobiological issues, mainly related to the RBE of high-LET radiation, are
discussed.
Proton beams bring a signicant improvement in the physical selectivity of the
treatment. The number of proton therapy centers in operation and in the planning stage
increases continuously worldwide. The best clinical results, so far, have been reported for
uveal melanoma, tumors of the base of skull, and some brain tumors in children.
Heavy ions are very promising by combining the advantage of the excellent physical
selectivity of protons with the radiobiological advantages of fast neutrons for some tumor
types. Heavy ions were applied at Berkeley from 1975 to 1992 and at NIRS in Chiba since
1994. A pilot study started at GSI-Darmstadt in 1997.
For historical reasons and for their general principles, pion therapy and the still
experimental Boron Neutron Capture Therapy are also briey discussed.
Besides the technological and radiobiological aspects considered here, other promising
approaches are now being investigated in the dierent therapy centers and research
laboratories worldwide in order to improve the eectiveness of radiation therapy. They
include better, individualized fractionation and time factor, association with drugs to
modulate the radiation sensitivity, combination with gene therapy and immunotherapy,
and protocols combining radiation therapy with surgery and chemotherapy in a more
eective way. These approaches are outside the scope of this chapter.
1. INTRODUCTION: RADIATION THERAPY (AND ION BEAMS)AN
EFFECTIVE APPROACH IN CANCER TREATMENT
1.1. Cancer Incidence and Social Implications
Radiation therapy constitutes, together with surgery and chemotherapy, one of the three
traditional and recognized methods of cancer treatment. In addition, novel approaches,
such as immunotherapy and gene therapy, are developing and appear to be promising.
With increased longevity of the populations resulting from improved control of
epidemic and infectious diseases, the frequency of cancerand the often associated suer-
inghas raised cancer awareness in the 20th century [1].
In developing countries, cancer cases have risen from 2 million in 1985 to 5 million in
2000 and are projected to number 10 million in 2015. By contrast, in developed countries,
there were 5 million cases in 1985 as well as in 2000; no increase is projected to 2015.
For example, in the United States, in 1991, more than 1 million invasive cancers
occurred, i.e., an incidence of about 400 per 100,000 per year. In addition, more than 600,000
nonmelanomatous skin cancers occurred; most of them can now be cured. In developed
countries, the probability of dying fromcancer is 2025%and is expectedto further increase.
1.2. Present Situation in Cancer Cure Rate
The dierent techniques mentioned abovesurgery, radiation therapy, and chemother-
apyare more and more frequently applied in combinations in modern protocols rather
than in competition. Today, about 45% of all cancer patients can be cured (Table 1) [2].
Radiation therapy contributes to the cure of 23%of all cancer patients [alone (12%) or
in combination with surgery (6%) or chemotherapy/immunotherapy (5%)]. Thus about half
of the cancer patients who are cured benet from radiation therapy at least for part of their
treatment: this proportion illustrates the important role of radiation therapy in cancer
management.
Sixty-ve percent of the cancer patients present themselves for the rst consultation
with a localized tumor. About 1/3 of these fail, i.e., nearly 25%of the total number of cancer
patients. This situation has to be improved mainly by improving the eciency of local
treatments, i.e., radiation therapy and/or surgery.
This is the challenge for the coming years for teams involved in development of new
radiation therapy modalities.
The importance of radiation therapy in the local control of primary or bulky cancers
will even increase in the future if more eective chemotherapeutic or systemic therapy (such
as immunology, gene therapy, etc.) becomes available to treat (prevent) metastatic disease.
Besides increasing the cure rate, it is important to improve the tolerance to the
treatment and reduce the long-termsequelae. Also, palliative treatments (in particular, pain
relief) deserve attention for those patients for whom there is no hope anymore of a cure.
1.3. Radiation Therapy in Cancer Treatment
At present, in industrialized countries, about 70% of the cancer patients are referred to a
radiation therapy department for at least part of the treatment. The majority of them are
treated with conventional photon beamtherapy (i.e., the reference treatment modality as
dened in Table 2.1).
Experience accumulated over more than a century indicates that the major improve-
ments in the eectiveness of radiation therapy were always associated with (or made possible
by) signicant progress in technology [35].
The major steps involved were rst the move from200-kVx-rays to cobalt-60 and then
to modern electron linear accelerators providing x-ray beams of about 20 MV(and electrons
when needed for some patients). Improvements in the beam penetration were, in general,
combined with improvements in beam delivery systems, e.g., isocentric gantries, variable
collimators, later on multileaf collimators, etc.
In addition, 3-D dosimetry and treatment planning were introduced and, last but not
the least, dramatic progress was achieved in imaging and related disciplines.
It is recognized that, besides the technological and radiobiological aspects considered
here, other promising approaches are nowbeing investigated in the dierent therapy centers
and research laboratories worldwide in order to improve the eectiveness of radiation
therapy. They include better individualized fractionation and time factor, association with
drugs to modulate the radiation sensitivity, combination with gene therapy and immuno-
therapy, and protocols combining radiation therapy with surgery and chemotherapy in a
more eective way. These approaches are outside the scope of this chapter.
Table 1 Summary of the Present Situation Concerning Cancer Cure Rate
Cure rate (%)
Patients appearing with localized tumor (65%):
Cured by surgery 22
Cured by radiotherapy 12
Cured by combination of surgery and radiotherapy 6
Patients appearing with inoperable or metastatic disease (35%):
Cured by combined complex treatment including, for example,
chemotherapy and immunotherapy
5
Total
a
45
a
Excluding nonmelanoma skin cancers.
Source: Ref. 2.
Before reviewing the results achieved with ion beams in cancer therapy, a short survey
of the general situation in radiation therapy and the main trends are presented in the next
section.
2. GENERAL TRENDS IN RADIATION THERAPY (IN RELATION WITH
TECHNOLOGICAL DEVELOPMENTS)
2.1. Conformal Radiation Therapy and Highly Selective and Novel
Photon Irradiation Techniques
For several decades, regular and continuous technical improvements were made to the linear
accelerators. Similar improvements were achieved in dosimetry and imaging, and, as a
consequence, the quality and eectiveness of the treatments progressively improved.*
Recently, dramatic and novel approaches were introduced in radiation therapy
planning and delivery: conformal radiation therapy, inverse treatment planning, and
intensity-modulated radiation therapy. These improved the optimization of all treatment
parameters in order to achieve the desired and optimal dose distribution, i.e., to match
(conform) as closely as possible the treated volume and the planning target volume (PTV)
and at the same time reduce the dose to the organs at risk (OAR). These techniques should
allow us to bring the conformity index close to unity [6,7]. This goal became possible due to
the contribution of (at least) the three following factors.
1. Patient data. Complete and accurate anatomical information, including the
location of the dierent target volumes and organs at risk, became possible with
the latest developments in modern imaging techniques, including computer to-
mography (CT), magnetic resonance imaging (MRI), positron emission tomog-
raphy (PET), etc. In addition, better knowledge of the natural cancer history
contributes to the selection of the optimum strategic approach (e.g., selection of
CTV, PTV, etc.).
2. Medical physics and dosimetry. Powerful and fast 3-D treatment planning, in-
cluding inverse planning with on-line 3-D dose computation, became avail-
able. Heterogeneities can be easily identied and appropriate corrections can be
applied. In addition, the radiation eld can be made to conform to irregular
contours and shapes of the organs.
3. Accelerator engineering. Full, reliable, and on-line control of the electron ac-
celerator, beam delivery system, and multileaf collimator is the basis of the new
conformal treatment and IMRT approaches. Patient-beam positioning became
more accurate and fully reliable.
Of course, appropriate QAprograms are required not only to check each of the above
three factors, but also to ensure that they are adequately combined.
From a technical point of view, intensity-modulated radiation therapy (IMRT)
optimizes several parameters: selection of multiple beams and, for each beam, optimization
of dose, dose rate, size and shape, etc. Tomotherapy optimizes the dose distribution by
IMRT in successive sections with immediate verication; gamma knife, cyberknife, and
radiosurgery concentrate high radiation doses in well-dened small volumes.
* The brachytherapy applications are not discussed in this chapter.
These new techniques are rapidly expanding and are becoming available in an
increasing proportion of hospitals, at least in industrialized countries. They are commer-
cially available. They constitute the most important trend in radiation therapy today.
2.2. Does Effectiveness of Photon Beam Therapy Reach a Plateau?
The energy of photons with their optimal beam penetration, the reliability of the beam
delivery and collimation systems, and the mechanical stability of the new generation of
accelerators have achieved a nearly optimum level of performance. Actually, with the
modern linear electron accelerators, it is now possible to irradiate at the prescribed dose
(nearly) any target volume of any shape with reduced irradiation of the surrounding organs
at risk (OAR).
However, the impressive development and progress in conformal therapy with
photons raise a dicult issue: to what extent has photon beam therapy reached a kind of
plateau as far as physical selectivity is concerned? This important question is still con-
troversial and heavily debated. If photon therapy had reached a plateau, the search for
improvements would be directed to alternative radiation modalities [8,9].
In particular, it is recognized that when optimizing the treatment parameters in order
to improve, e.g., the conformity index in conformal therapy or IMRT, other indices can
change adversely, for example, the size of the irradiated volume, the integral dose, and the
dose homogeneity throughout the PTV.
2.3. New Types of Radiations
An alternative to further improve or optimize the photon techniques is to replace the con-
ventional photonbeams withnewtypes of radiation. Indeed, since the beginning of radiation
therapy, the radiation oncologists have always been eager to search new types of beams
(dierent from conventional x-rays/photons) in order to improve the ecacy of radiation
therapy. In principle, dierent approaches can be adopted (Table 2).
Improving the physical selectivity. The most straightforward method to improve the
ecacy of radiation therapy is to improve the physical selectivity of the irradiation, i.e., by
using beams with better physical characteristics (penetration, collimation, etc.). This is the
rationale for the introduction of proton beams: no radiobiological advantage is expected.
Improving the radiobiological dierential eect between the cancer and normal cell
populations. This second approach is more complex and involves radiobiological consid-
erations. New and dierent radiation qualities have been considered such as high-LET
radiations. Some of the radiobiological issues involved in the use of high-LET radiation, in
particular the RBE concept, are discussed in Sec. 3.
Table 2 New Types of Beams in Radiation Therapy (Alternative to Conventional Photon
Beam Therapy)
(1) Improving the physical selectivity: proton beams
(2) Improving the radiobiological dierential eect: fast neutrons and other high-LET radiations
(3) Combination of physical selectivity and radiobiological dierential eect: heavy ions
Among high-LET radiations, fast neutrons were rst introduced to exploit a radio-
biological dierential eect; no benet is expected from the physical selectivity.
However, clinical evidence has demonstrated that, from a pure safety point of view, a
physical selectivity at least as good as that obtained with conventional photon beams is
absolutely required for neutrons as well.
The logical combination of these two approaches is the rationale for the application of
heavy ions. The use of heavy ions in cancer therapy is, in principle, easy to justify by several
sets of physical and radiobiological arguments. However, heavy ions are expensive, require
sophisticated quality assurance, and raise complex radiobiological and physical issues as
long as robust clinical data are not yet available.
The specic techniques of brachytherapy and the administration of unsealed sources
of radionuclides, in nuclear medicine [10], are not dealt with in this chapter.
2.4. Reference Treatment Modality
Evaluation of the relative merits of dierent treatment techniques or strategic approaches
existing or newly introducedrequires the denition of a reference treatment modality.
Fractionated photon beam therapy, as dened in Table 3, is generally accepted as the
reference therapy modality. This is due to its broad application, the experience accumulated
over several decades, and its recognized eectiveness [4,5,8].
However, when making these comparisons, a diculty arises from the fact that the
eciency of photon therapy (i.e., the reference) is improving continuously, as clearly
shown above (Sec. 2.1) [9].
3. HIGH-LET RADIATION AND RBE: RADIOBIOLOGICAL CONCEPT
AND CLINICAL APPLICATION
3.1. From Absorbed Dose to Biological Effects
Absorbed dose is a scientically rigorously dened quantity which is used to quantify the
exposure of humans, biological systems, and any type of material to ionizing radiation.
The concept and quantity absorbed dose were introduced by the ICRU in 1951,
with the special unit rad. A new special unit gray (Gy) was introduced in 1972 to be in
correspondence with the SI system of quantities and units (Syste` me International des
Grandeurs et Unite s) [11,12].
Absorbed dose is a fundamental and basic physical quantity which can be used in all
elds where ionizing radiations are used. It is directly related to the physical, chemical, and
biological eects produced by the irradiation. The concept of absorbed dose thus has broad
applications and is indeed widely used. Metrological institutions provide standards and
calibration of instruments in terms of absorbed dose.
Table 3 The Reference Radiation Therapy Modality
External photon beam therapy, involving (multiple) beams of conformally adjusted size and shape,
adequately orientated to cover the PTV(s) in a homogeneous way, with photon energy ranging
from a few megavolts to about 20 MV, using fractionated irradiation with daily fractions of 2 Gy,
ve times a week, over 467 weeks depending on the clinical situation.
Although the biological eect is directly related to the quantity absorbed dose, there is
no unique relationship between absorbed dose and induced biological/clinical eects, and
other factors have to be considered, such as:
1. Radiation quality
2. Dose rate, fractionation, and temporal distribution of the irradiation
3. Level of biological eect/endpoint
4. More generally, the technical conditions in which radiological treatment is de-
livered (resulting in dierent dose distributions and dierent doses to normal
tissues)
Aweighting factor or weighting function, W, thus is applied to correlate and link
absorbed dose and biological eect [13,14]. The factors listed above aect the weighting
function or weighting factors independently. Dierent empirical formulations are used in
radiation therapy to express this biological weighting function. Some agreement has been
reached on the numerical values of the involved quantities, but only for well-established
radiotherapy techniques.
3.2. Energy Distribution at the Microscopic Level, Microdosimetry,
and Biological Efficiency
Radiation quality is dened by the nature, charge, and energy spectrum of the particles and
can be characterized by the linear energy transfer (LET) or, alternatively, by the micro-
dosimetric spectra at the point of interest under the actual irradiation conditions.
With hadrons (i.e., neutrons, protons, and heavy ions), new radiation qualities are
introduced in therapy. The distributions of the ionizations (and energy deposition events)
along the particle tracks are dierent, and, as a result, dierent and increased biological
eects (at equal absorbed dose) may be expected compared with the conventional photon
beams. Fig. 1 illustrates the dierences in dose necessary to produce a given biological eect
as a function of radiation quality [15].
Fig. 2 illustrates schematically the distribution of the ionizations along the particle
tracks after photon and neutron irradiation [1,16]. In a more quantitative way, Fig. 3
presents the microdosimetric lineal energy, y, spectra for two clinical fast neutron beams: the
highest and lowest energy used in cancer therapy (measurements performed at Louvain-la-
Neuve and Essen, respectively) [17].
These large dierences in energy distribution, at the microscopic level, between
radiation qualities at equal absorbed dose, produce dierent biological eects: this leads
to the concept of RBE.
3.3. The RBE Concept
The concept of relative biological eectiveness (RBE) was introduced by the ICRP and the
ICRU [18,19].
The RBE is dened as a dose ratio, between two doses delivered with two radiation
qualities, which produces the same eect on a given biological system, under the same
conditions.*
* If A is the test radiation quality and B is the reference radiation quality, and if D
A
and D
B
are
the doses necessary to produce the eect of interest with radiation A and B, respectively, the RBE
of radiation A, relative to radiation B, is D
B
/D
A
.
Figure 1 Absorbed dose necessary to produce a given biological eect on a given system, in the
present case: 50% inactivation of V79 hamster cells in exponential growth phase. The dose needed
depends on the type of the particles (photons, alpha particles, or uranium ions) and on their energy.
(From Ref. 15.)
Figure 2 Distribution of ionizations in a mediumirradiated by x-rays (a) and neutrons (b). The black
dots represent the ionizations produced along the tracks of electrons set in motion by x-rays (a) and of
protons, a-particles, or heavy ions set in motion by neutrons (b). The distribution of ionizations is very
dierent. After irradiation by neutrons, when a vital sensitive structure (or target, represented by the
circles) is crossed by a track, the deposition of energy (or the damage) is so great that there is a high
probability of cell death whatever the cell line, the position in the cell cycle, the degree of oxygenation,
etc. After irradiation by x-rays, the energy depositions are smaller and more variable. In some cases, a
single particle deposits enough energy to kill the cell; in others, death of the cell requires the
accumulation of damage produced by several tracks. (From Ref. 16, adapted in Ref. 3.)
The RBE is a clear, unambiguous, and well-dened radiobiological concept. A RBE
value is the result of an experiment and is thus associated with an experimental uncertainty.
The biological system, type, and level of eect, the dose, and the experimental conditions in
which a given RBE value has been obtained must be specied.
3.4. RBE Values and Modifying Factors
The RBE of a given radiation quality relative to
60
Co gamma rays is not a unique value but
varies to a large extent with dose, biological system, and eect.
Fast neutrons are selected here as an example to illustrate the RBE variations because
their RBE variations are signicant and are well documented. They can be summarized as
follows (Figs. 4 and 5) [20,21]:
1. RBE values range within large limits (from less than 2 up to about 10).
2. The RBE increases with decreasing dose.
3. The RBE values for late eects are signicantly higher than for early eects
(Figs. 4 and 5).
4. The RBE of the fast neutron beams used in therapy varies with energy, and this
variation is signicant (Fig. 6) [22].
Figure 3 Comparison of energy depositions after irradiation with fast neutrons and x-rays. The
curves indicate distributions of individual energy-deposition events in a simulated volume of tissue 2
Am in diameter; the parameter y (lineal energy) represents the energy deposited by a single charged
particle traversing the sphere, divided by the mean cord length. The maximumwith x-rays is at 0.3 keV
Am
1
and with d(14)+Be neutrons at 20 keV Am
1
. The spectrum for p(65)+Be neutrons shows 4
peaks: the rst is at 8 keV Am
1
and corresponds to high-energy protons, the second at 100 keV Am
1
corresponds to low-energy protons, the third at 300 keVAm
1
is due to a-particles, and the last, at 700
keV Am
1
, is due to recoil nuclei. (From Ref. 17.)
Figure 4 RBE/dose relationships for dierent normal tissues. Summary of the pretherapeutic
radiobiological experiments performed at the Hammersmith cyclotron with d(16)+Be neutrons. The
increase of RBE with decreasing dose is obvious for all tissues investigated. (From Ref. 20.)
Figure 5 RBE/dose relationships for 15-MeV neutrons produced by a (d,T) generator. Dierent
biological endpoints in normal tissues and tumors are investigated. For late tolerance of spinal cord,
the RBE increases from 1.2 to 3.7 when the neutron dose per fraction decreases from 16 to 0.8 Gy.
Higher RBE values were found later on for spinal cord at lower doses. (From Ref. 21.)
Ahigh RBE of a new radiation quality does not per se imply a therapeutic advantage.
The therapeutic gain is actually the ratio of the RBE for the eects on the cancer cell
population and the RBE for the eects on the normal tissues (under the actual irradiation
conditions).
Further information about the RBE and the specic biological eects of the dierent
hadrons used in therapy are found in Sec. 4.
3.5. From Radiobiology to Clinical Application of RBE: The RBE Weighting
Factor, W
RBE
When prescribing the dose in hadron (neutron) therapy, the radiation oncologist has to take
into account the (set of) reported RBE values, and, from them, the radiation oncologist has
to select one RBE value to weight the absorbed dose in order to obtain the desired clinical
eect [13,14].
Figure 6 RBE variation of neutron beams as a function of energy. The p(65)+Be beamof Louvain-
la-Neuve is taken as reference (RBE = 1). The closed squares and circles correspond to six dierent
visited neutron facilities. The open squares and circles correspond to beams produced at the variable-
energy cyclotron of Louvain-la-Neuve. On the abscissa, the eective energy of the neutron beams is
expressed by their half-value thickness (HVT 5/15) measured in specied conditions. Intestinal crypt
regeneration in mice, after a single fraction irradiation, is taken as the biological system. The 95%
condence intervals are shown. A straight line is tted through the points (squares) corresponding to
neutron beams produced by the (p+Be) reaction. For comparison, the neutron beams produced by the
(d+Be) reaction are represented by circles. (From Ref. 22.)
This value is, in a strict sense, no longer a RBE but a weighting factor (selected of
course on the basis of RBEdata) applied to compensate for RBE dierences/variations. It is
the RBE weighting factor, W
RBE
.
It is current medical practice to select the weighting factors as a function of two main
criteria: (1) late tolerance in normal tissues and (2) in relation to a daily fractionation of 2 Gy
(photons or
60
Co-gamma rays). Therefore among the published RBEvalues, those obtained
for late eects on normal tissues, with 2 Gy of photons per fraction as reference, are the most
relevant for the selection of the RBE weighting factor and could be dened as reference
conditions. The reference RBE is then, to some extent, an average or overall RBE for
late tolerance of normal tissues at risk, evaluated vs. 2 Gy per fraction of photon radiation.
The reference RBE provides a rst indication to select the RBE weighting factor
W
RBE
. However, other factors, which are not always clearly identied, may also inuence
the selection of the RBE weighting factor:
1. Past personal clinical experience
2. Clinical experience reported from other centers
3. Some dierences in time factors
4. Some volume eects related to the beam characteristics, geometry, or technical
conditions
Selection of the RBE weighting factor, W
RBE
, implies the (informed) judgment and
clinical experience and thus the responsibility of the radiation oncologist in charge of the
patient.
This RBE weighting factor has been called clinical RBE in the past; this termi-
nology may be confusing.
3.6. The Biologically Weighted Dose for RBE, D
RBE
The product of the neutron absorbed dose D by W
RBE
is the biologically weighted dose
for RBE, D
RBE
:
D
RBE
DW
RBE
where D and D
RBE
are expressed in Gy but a subscript may be useful to avoid confusion
between the (physical) absorbed dose D and the biologically weighted dose D
RBE
.
In collaborative studies involving several neutron therapy centers, the same bio-
logically weighted doses D
RBE
should be prescribed. If the participating centers use neutron
beams with dierent RBEs, dierent W
RBE
values thus have to be introduced and dierent
(physical) neutron doses have to be prescribed.
In addition to D
RBE
, the delivered absorbed doses and the selected RBE weighting
factors W
RBE
should always be reported, in addition to D
RBE
, to allow for eventual later
reevaluation of the results [23].
A similar approach can be followed with protons and heavy ions. There is an
additional diculty with heavy ions (e.g., carbon ions or neon ions) because the RBE varies
signicantly with depth in the tissues (see Sec. 4.4). With proton beams, there are only
discrete RBE variations (less than 1020%) (see Sec. 4.2).
3.7. Discussion
Absorbed dose has proven to be a fundamental and very useful quantity in radiation therapy
which should always be reported. However, absorbed dose alone cannot predict the
biological eects, and dierent weighting factors have to be introduced depending on the
radiation therapy modality.
In external photon beam therapy, weighting factors, W
a/h
, are currently estimated
based on the a/h model to compensate for dierences in fractionation.
In brachytherapy, with the modern equipment now available, the clinically applied
dose rates vary within large limits. The ICRU and the international brachytherapy com-
munity are recommending weighting factor, W
HDR
and W
PDR
, to compensate for the
dierences in dose rate for high dose-rate (HDR) and pulse dose-rate (PDR) brachytherapy,
respectively.
In hadron therapy, a similar approach and symbolism are presented to take into
account the RBE dierences. RBE values for neutrons are well documented, and reliable
data are now becoming available for protons and heavy ions, on which safe weighting
factors W
RBE
can be based. Besides radiobiological determinations, microdosimetry brings
independently additional information on the radiation quality and improves condence in
both sets of data. Microdosimetry provides an objective description of the radiation quality
at the point of interest under the actual irradiation conditions. Correlation between this set
of information and the experimental RBE results is of great scientic and clinical value in
hadron therapy [24,25].
For the dierent therapy modalities, the products of the absorbed doses by the
biological weighting factors (W
a/h
, W
HDR
, W
PDR
, and W
RBE
) are the biologically weighted
doses (D
a/h
, D
HDR
, D
PDR
, and D
RBE
, respectively). They are expressed in Gy like the
absorbed dose, but, to avoid confusion, subscripts (Gy
a/h
, Gy
HDR
, Gy
PDR
, and Gy
RBE
)
must indicate that the absorbed doses have indeed been weighted.
The biologically weighted dose is a quantity intended to be correlated, as closely as
possible, to the relevant biological/clinical eect. However, in all radiotherapy reports, the
(physical) absorbed doses D and the biological weighting factors (W
a/h
, W
HDR
, W
PDR
,
W
RBE
, etc.) should always be indicated separately and not just the biologically weighted
doses (D
a/h
, D
HDR
, D
PDR
, D
RBE
, etc.).
The weighting factors, W, as introduced above, aim to be a pragmatic approach to
harmonize prescription and reporting of radiation treatments. They are based on actual
clinical practice, current techniques, and available radiobiological data. Their use should be
limited to the technical treatment modality for which they were designed. They are not
universally applicable factors, and they should not be multiplied or combined between
each other.
Finally, it must be stressed again that the selected weighting factors W (and thus the
biologically weighted doses) are based on available radiobiological data and clinical
observation, but they always imply clinical judgment and experience.
4. NONCONVENTIONAL RADIATION THERAPY MODALITIES
(RATIONALE, TECHNICAL ASPECTS, AND SHORT SURVEY
OF CLINICAL DATA)
4.1. Fast Neutron Therapy
Rationale: Radiobiological Basis
Fast neutrons were the rst nonconventional radiations to be used in clinical radiation
therapy. The pioneering work in fast neutron therapy was performed by Stone [26] and
his associates at Berkeley between 1938 and 1943. In the late 1960s, after extensive
radiobiological experiments, a neutron therapy program was initiated at the Hammersmith
Hospital in London and, a few years later, in several centers in Europe and in the United
States [27,28].
The radiobiological rationale for introducing high linear energy transfer (LET) ra-
diation in cancer therapy, as proposed in the 1960s, is still valid and has not been con-
tradicted by more recent radiobiological ndings [3].
The radiobiological and clinical data obtained with fast neutrons are reviewed in the
following section; they deserve a detailed and careful analysis as they constitute the rationale
of the clinical application of any high-LET radiation and, in particular, the justication of
the modern heavy-ion therapy programs.
The dierences in the radiobiological eects produced by low- and high-LET ra-
diations are related to the pattern of energy distribution at the level of the particle
tracks. The distributions of energy (or ionizations) at the microscopic level after low- and
high-LET radiation exposure are compared in Figs. 2 and 3 [16,17,29]. For fast neutrons,
at the energies used in therapy, the energy deposited in a 2-Am sphere by one particle
track (proton) is 50 to 100 times higher than after gamma-ray irradiation (secondary
electrons). Such dierences result in relative biological eectiveness (RBE) of neutrons
higher than unity (ranging between 3 and 5) and in dierent shapes of the doseeect
relationships.
The arguments for using high-LETradiation in cancer therapy are based on these well-
established dierences in energy distribution at the microscopic level and can be summarized
as follows:
A reduction in the oxygen enhancement ratio (OER) with increasing LET
A reduction of the dierences in radiosensitivity related to the position of the cell in
the mitotic cycle
Less repair and thus less clinical relevance of the dierent repair mechanisms
Historically, the oxygen eect was the main rationale for introducing fast neutrons in
radiotherapy. Three sets of data support this rationale:
1. Hypoxic cells are present in the malignant tumors; they result from the fast
proliferation of the cancer cells.
2. Hypoxic cells are three times more radio-resistant than well-oxygenated cells
(OER = 3) for low-LET radiation. The presence of a small percentage of hy-
poxic cells (1% or even 0.1%) can thus make the tumor radio-resistant.
3. The OER decreases when LET increases (Fig. 7) [30]. It decreases to about 1.6
for fast neutrons and is close to unity for alpha particles. OER = 1.3 and 1.0 for
alpha particles of 4 and 2.5 MeV (i.e., for 110 and 160 keV/Am), respectively.
Fig. 8 illustrates howincreasing LET reduces the dierences in radiosensitivity related
to the position of the cells in the mitotic cycle [31]. Cells in stationary phase and in S phase
are signicantly more radio-resistant than mitotic cells.
Lastly, because of the large amount of energy deposited in the critical cellular target by
a single high-LET particle track, repair of sublethal damage is reduced (or less relevant).
High-LET radiation is thus particularly ecient against cells which have a high capability
for repair of sublethal damage. Therefore the dose per fraction is less important with the
high-LET than with the low-LET radiation, which gives the radiation oncologist more
freedom in the selection of the fractionation scheme.
The radiobiological arguments discussed above indicate that the high-LET radiation
could bring a benet in the treatment of some cancer types. However, they also imply
the need for the development of predictive tests, allowing the radiation oncologist to
select the best radiation quality (low or high LET) for a given patient group or individual
patient.
The observations of Battermann et al. [32] on lung metastases indicate that slowly
growing tumors (well dierentiated) could benet from high-LET treatment (Fig. 9). The
clinical results accumulated over more than 25 years conrmed these observations.
Technological Aspects
Many centers, including 15 in Europe (former Soviet Union excluded), have applied fast
neutron therapy using dierent types of generators, which can be schematically distributed
into four groups:
Reactors, using fast neutrons in the beam (limited application)
Low-energy cyclotrons, using mainly incident deuterons with energies ranging
from 13 to 16 MeV (d+Be reaction)
(d+T) generators
High-energy cyclotrons or linear accelerators (d/p+Be reaction)
Figure 7 Survival curves of human kidney cells T1 irradiated under hypoxic and aerobic conditions
with dierent qualities of radiation: (a) 250-kV x-rays (LET of about 1.3 keV Am
1
); (b) 14-MeV
neutrons produced by the (d,T) reaction (LET of about 12 keV Am
1
); (c) 4-MeV a-particles (LET =
110 keV Am
1
); (d) 2.5-MeV a-particles (LET = 166 keV Am
1
). (From Ref. 30.)
Figure 8 Dierences in radiosensitivity with the position of the cells in the mitotic cycle. The
dierences are reduced with increasing LET. Single-hit inactivation coecients (a) for homogeneous
populations of mitotic, G1-phase, and stationary phase Chinese hamster cells irradiated with 220-kVx-
rays and various charged particle beams, as a function of median LET (in keV Am
1
). (FromRef. 31.)
Figure 9 Relation between the RBE of neutrons for regression of lung metastases in patients and
their doubling time. The closed circles correspond to measured values of RBE. The open circles
correspond to values estimated fromirradiation with neutrons only. For the 15-MeVneutrons used in
this study [produced by a (d,T) generator], the RBE for the tolerance of the most important normal
tissues is about 3. As a consequence, neutrons are a good indication (RBE>3) for tumors having
doubling times greater that c100 days. Incontrast, they shouldnot be usedfor rapidly growing tumors.
(From Ref. 32.)
Only for the fourth group can the physical selectivity and the technical conditions be
considered to be sucient (or nearly sucient) for adequate treatments, especially in com-
parison with modern linear accelerators.
In some centers, large clinical programs were completed from which important radio-
biological and clinical conclusions could be derived. In some other centers, the facilities were
shut down abruptly:
In most centers, due to technical diculties; for example, all (d+T) generators are
now shut down.
In other centers, due to patient recruitment problems.
In general, due to suboptimal physical selectivity.
Today, in the majority of centers still active in neutron therapy, the technical con-
ditions are becoming progressively comparable to those in modern photon beamtherapy. In
addition, a few new high-energy facilities have been proposed (e.g., in China, Germany,
Poland, Slovakia, and South Africa).
Clinical Aspects (Short Survey)
Salivary gland tumors and locally extended prostatic adenocarcinoma were proven to be an
indication for fast neutrons.
Salivary Gland Tumors. Neutron beam therapy should be considered as the treat-
ment of choice in patients with unresectable malignant salivary gland tumors or in patients
where radical resection would require facial nerve sacrice (Table 4) [33].
For inoperable primary or recurrent tumors, a randomized cooperative study showed,
at 2 years, a signicant advantage for neutrons compared to photons for loco-regional
control (76% vs. 17%, P<0.005) and a trend towards improved survival (62% vs. 25%).
Ten-year analysis continued to show a striking dierence in loco-regional control (56% for
neutrons vs. 17% for photons, P = 0.009), but both groups experienced a high rate of
metastatic failure (Fig. 10) [34].
Prostatic Adenocarcinoma. For prostatic adenocarcinomas, their typical slow
growth rate and lowcycling fraction provide a logical radiobiological rationale for exploring
neutrons (high LET) in the treatment of this disease.
Table 4 Pooled European Data of Local Control in Advanced Salivary
Gland Tumors
Reference No. of patients Local control
Catterall (1987) 65 48 (74%)
Battermann and Mijnheer (1986) 32 21 (66%)
Duncan et al. (1987) 22 12 (55%)
Prott et al.(1996) 64 39 (61%)
Kova cs et al. (1987) 15 13 (87%)
Kru ll et al.(1995) 74 44 (59%)
Skolyszweski et al. (1982) 3 2
Overall 275 179 (65%)
Source: Ref. 33.
The Radiation Therapy Oncology Group (RTOG), 1997, compared mixed beam (a
combination of photons and neutrons) to conventional photons for locally advanced
prostatic cancer. Loco-regional control as well as survival were signicantly superior after
mixed-beam irradiation (Fig.11) [34].
In 1986, the Neutron Therapy Collaborative Working Group (NTCWG) compared
neutrons (alone) and conventional photons. Asignicant dierence ( P<0.01) was observed
in clinical loco-regional failure, with actuarial 5-year failure rates of 11% vs. 32% after
neutrons and photons, respectively (Fig. 12) [34]. Inclusion of routine posttreatment
biopsies resulted in 5-year histological localregional failure rates of 13% and 32%,
respectively ( P = 0.01).
Due to the long natural history of recurrent prostate cancer, longer follow-up is
required to assess the ultimate impact of the improved local control on survival. However,
the prostate specic antigen (PSA) levels could provide an indication: at 5 years, 17% of
the neutron patients showed elevated PSA levels compared to 45% for the photon patients
( P<0.001).
Late sequelae (mainly large bowel complications) were worse in the neutron-treated
group (11% vs. 3%). However, no colostomy was required in 51 patients treated with a
multileaf collimator at the University of Washington, while 6/38 patients, fromother centers
using movable jaw or xed cone collimator, required colostomy.
The data from Louvain-la-Neuve suggest that mixed neutronphoton therapy is
particularly ecient in patients with unfavorable prognostic factors, such as PSA >20
ng/mL [35].
Other Tumor Sites or Types. For other tumor sites or types, such as slowly growing
soft tissue sarcomas, xed lymph nodes in the cervical area, locally extended antrumtumors,
and some bronchus carcinomas, the available clinical results tend to show a benet with
neutrons. However, they need to be conrmed by randomized studies [5,28,36].
Figure 10 Neutron therapy of salivary gland tumors. Probability of localregional failure for
unresectable salivary gland tumors. Starting values of the curves represent initial localregional
failure rates. (From Ref. 34.)
4.2. Proton Beam Therapy
Proton beam therapy was a signicant step towards better physical selectivity, and it is the
most straightforward approach to improve the ecacy of therapeutic irradiations.
The rst cyclotron was built by Ernest O. Lawrence in 1932, and since 1938, cyclotrons
have been used for patient treatment. In Berkeley, in 1954, the rst human target irradiated
with protons was the pituitary gland with the aim to suppress its function for slowing down
the metastatic development of breast cancer.
Figure 11 Clinical loco-regional control in patients treated with mixed (neutron/photon) beams or
photons only (RTOG randomized trial) for locally extended prostatic adenocarcinoma. (From Ref.
34.)
Figure 12 Actuarial clinical loco-regional failure in patients with locally advanced prostate cancer.
Results of NTCWG trial on prostate. (From Ref. 34.)
Today, proton beam therapy is applied in more than 20 centers worldwide and new
facilities are in preparation (or under discussion). So far, about 30 000 patients have been
treated with protons (Tables 5a and 5b). There is a continuously increasing number of
proton therapy centers in operation and an impressive number of projects under construc-
tion or study.
On the other hand, proton beams have no radiobiological advantages and a constant
relative biological eectiveness (RBE) with respect to photons of 1.01.1 is generally
assumed. The vast clinical experience accumulated with photons can thus be transferred
directly to proton therapy.
Rationale: The Bragg Peak
The depthdose curve in a proton beamexhibits a characteristic shape. The absorbed dose is
low at the entrance (initial plateau), then increases in depth more and more steeply, to
Table 5a Worldwide Charged Particle Patients Totals (HTCOGHadron Therapy Cooperative
Group; Janet Sisterson, 2001)
Who Where What
Date
1st RX
Date
last RX
Recent
patient total
Date
of total
Berkeley 184 California, U.S.A. p 1954 1957 30
Berkeley California, U.S.A. He 1957 1992 2054 Jun. 1991
Uppsala Sweden p 1957 1976 73
Harvard Massachusetts,
U.S.A.
p 1961 8747 Jan. 2001
Dubna Russia p 1967 1974 84
Moscow Russia p 1969 3268 Jun. 2000
St. Petersburg Russia p 1975 1029 Jun. 1998
Berkeley California, U.S.A. HI 1975 1992 433 Jun. 1991
Chiba Japan p 1979 133 Apr. 2000
PMRC, Tsukuba Japan p 1983 629 Jul. 1999
PSI (72 MeV) Switzerland p 1984 3253 Dec. 2000
Dubna Russia p 1987 79 Dec. 2000
Uppsala Sweden p 1989 236 Jun. 2000
Clatterbridge England p 1989 999 Jun. 2000
Loma Linda California, U.S.A. p 1990 5638 Dec. 2000
Louvain-la-Neuve Belgium p 1991 1993 21
Nice France p 1991 1590 Jun. 2000
Orsay France p 1991 1894 Jan. 2001
N.A.C. South Africa p 1993 380 Nov. 2000
MPRI Indiana, U.S.A. p 1993 34 Dec. 1999
UCSF-CNL California, U.S.A. p 1994 284 Jun. 2000
HIMAC, Chiba Japan HI 1994 745 Dec. 1999
TRIUMF Canada p 1995 57 Jun. 2000
PSI (200 MeV) Switzerland p 1996 41 Dec. 1999
GSI Darmstadt Germany HI 1997 72 Jun. 2000
HMI, Berlin Germany p 1998 166 Dec. 2000
NCC, Kashiwa Japan p 1998 35 Jun. 2000
3304 Ions
28,700 Protons
Total 33,104 All particles
reach a maximum at the level of the Bragg peak (Fig. 13). The depth of the Bragg peak in
the tissues depends on energy. There is no dose beyond the depth of the Bragg peak and thus
full sparing of the tissues behind the target volume.
The Bragg peak has to be spread over the depth occupied by the planning target
volume [spread-out Bragg peak (SOBP)] (Fig. 14).
Technological Aspects: Beam Delivery
In the past, proton therapy was performed with complex physics machines, adapted to
clinical needs, not always available full time, often expensive to maintain, and dicult to
tune. Today, several commercial companies oer turn key equipment for proton therapy,
adapted to the needs (or to the nancial limitations) of the center. It is likely that this trend
will develop further.
The establishment of the Northeast Proton Therapy Center (NPTC) in Boston was
obviously the trigger of the movement, but such a fast proliferation was certainly not
expected [37].
In general, a new radiotherapy technique may be considered to have gained its place
among the other ones when the equipment can simply be purchased commercially. This is
obviously now the case with proton therapy.
From a technical point of view, two methods can be used to deliver proton beam
therapy: passive scattering and scanning beam (Fig. 15). The use of a scanning beam is a
more complex approach, but it allows close matching of the treated volume with the PTV. In
Table 5b Charged Particle New Facilities (HTCOGHadron Therapy Cooperative Group;
Janet Sisterson, 2001)
Institution Place Type 1st
INFN-LNS, Catania Italy p 2001
NPTC (Harvard) Massachusetts, U.S.A. p 2001
Hyogo Japan p, ion 2001
NAC, Faure South Africa p 2001
Tsukuba Japan 2001
Wakasa Bay Japan 2002
Bratislava Slovakia p, ion 2003
IMP, Lanzhou P.R. China CAr 2003
Shizuoka Cancer Center Japan 2003
Rinecker, Munich Germany p 2003?
CGMH, northern Taiwan Taiwan p 2001?
Erlangen Germany p 2002?
CNAO, Milan and Pavia Italy p, ion 2004?
Heidelberg Germany p, ion 2006
AUSTRON Austria p, ion ?
Beijing China p ?
Central Italy Italy p ?
Clatterbridge England p ?
TOP project ISS Rome Italy p ?
Three projects in Moscow Russia p ?
Krakow Poland p ?
Proton Development N.A. Inc. Illinois, U.S.A. p ?
PTCA, IBA United States p ?
Figure 13 Depthdose curves for proton beams of dierent energy. The position of the Bragg peak
depends on energy and can thus be adjusted according to the clinical requirements. (From PSI,
Villigen, courtesy of Pedroni and Scheib.)
Figure 14 Proton beam irradiation of a deep-seated large tumor. Single Bragg peaks of dierent
energy are combined, in adequate proportions, to obtain a homogeneous dose distribution at the
level of the SOBP. The depthdose curve of a photon beam, shown for comparison, is inferior
compared to the proton curve. However, an optimized multield photon treatment allows to reach
better irradiation conditions. (From Ref. 43.)
Europe, the Paul Scherrer Institute (PSI), Villigen, Switzerland has developed (and is
planning to further improve) a highly sophisticated beamscanning systemin order to exploit
all the physical advantages of the proton beams. The scanning beam technique will be dealt
with in more detail in the section on heavy ions (Sec. 4.4).
Of course, like with photons, several intersecting proton beams can be used in order
to further improve the nal dose distribution. Fixed beams or an isocentric gantry can
be used.
Clinical Aspects (Short Survey)
The clinical results available so far can be summarized as follows [2,5].
Uveal Melanoma. Charged particle beams and, in particular, protons are ideal for
treating intraocular lesions since they can be made to deposit their absorbed dose in the
target volume, while signicantly limiting the irradiation of the noninvolved ocular and
orbital structures (Fig. 16).
Large series of patients with uveal melanoma were treated with protons in several
centers worldwide. The Massachusetts General Hospital/Harvard Cyclotron Laboratory
(MGH/HCL) in Boston played a pioneering role, and 2568 uveal melanoma patients were
treated through September 1998 [38].
Local control of the tumor within the treated eye which was 96%and 95%at 60 and 84
months, respectively, was reported. Eye retention probability after proton therapy depends
on tumor size, being 97%, 93%, and 78% for patients with small, intermediate, and large
tumors, respectively. Survival at 5 years of the patients treated with protons or enucleation is
similar (about 80%).
Tumors of the Base of Skull and Cervical Spine. Proton or other charged particle
beams are a treatment of choice for skull base and cervical spine tumors: irradiation can be
Figure 15 Schematic representation of a purely passive spreading system. A set of scatterers
guarantees a at transverse dose distribution over a large eld. Starting with a single Bragg peak, a
ripple lter (in combination with a at energy degrader as range shifter) produces a SOBP with a
homogeneous dose at each depth. A special compensator conforms the distal surface of the radiation
eld with the shape of the planning target volume. (From Ref. 43.)
focused in the target volume, while achieving signicant sparing of the brain, brain stem,
cervical cord, optical nerves, and chiasma.
At HCL/MGH in Boston, 621 patients with chordomas and low-grade chondrosar-
comas of the skull base and cervical spine were treated with protons between 1975 and
January 1998. For skull base tumors, with follow-up ranging from1 to 254 months (median
of 41 months), local recurrence-free survival is signicantly better for chondrosarcomas
than for chordomas. It is 98%at 5 years and 94%at 10 years for chondrosarcomas and 73%
at 5 years and 54% at 10 years for chordomas (Fig. 17) [39]. Overall survival is also
signicantly better: 91% vs. 80% at 5 years and 88% vs. 54% at 10 years, respectively.
For cervical spine tumors, with follow-up ranging from1 to 172 months (median of 36
months), local recurrence-free survival was not signicantly dierent for chondrosarcomas
and chordomas: 54% vs. 69% at 5 years and 54% vs. 48% at 10 years, respectively. The
overall survival at 5 years for chondrosarcomas and chordomas were 48% and 80%,
respectively, but at 10 years, 48% and 33%, respectively [38].
CNS Tumors in Children. Pediatric tumors located in the CNS are particularly
challenging and deserve highly rened techniques of radiation therapy like proton therapy
(Fig. 18) [4042]. The preliminary results from Loma Linda, MGH/HCL, and Centre de
Proton The rapie dOrsay are promising and showan excellent immediate and late tolerance.
The reduced integral dose may be of particular importance in the pediatric population.
Other Localizations. Results of proton beam therapy for other tumor types and
localizations have been reported, in particular, for retinoblastoma and age-related macular
degeneration [2]. In the pioneering centers, patient selection, special care applied to each
treatment, as well as expertise of the multidisciplinary clinical teams make it dicult to
conclude whether the excellent results were due to the protons themselves or reect the
expertise of the dierent teams.
Figure 16 Proton therapy for uveal melanoma. Dose distribution obtained with a beam of 60-
MeV protons with an appropriate spread-out Bragg peak (energy modulated from 1460 MeV).
Transverse section through the center of the eye. The position of the tumor [gross tumor volume
(GTV)] is indicated by the posterior hatched area. Protons allow to obtain a homogeneous dose over
the whole GTV with eective sparing of the normal structures. This implies a great precision in
patient-beam positioning. (Courtesy from PSI, cited in Ref. 3.)
4.3. Pion Therapy
Between 1974 and 1994, 1100 patients were treated with negative pions at three centers.
These particles, which provide a mixture of high- and low-LET components and some
physical selectivity advantage, were very expensive to generate and the clinical results were
unconvincing. All three facilities have now been closed down [5].
4.4. Heavy-Ion Therapy
Introduction: Terminology
Strictly speaking, hadrons include protons, neutrons, and mesons, but, in the context of
hadron therapy, it is common practice to include (charged) ions heavier than protons and
often to exclude neutrons. As seen above (Sec. 4.3), k-mesons are no longer used in therapy.
In the radiation oncology (or radiobiology) community, hadron therapy currently
includes the application of protons, helium, carbon, neon, and argon ions. Carbon, neon, or
argon ions are called heavy ions, while protons and heliumions are called light ions. In
contrast, in the physics community, all ions mentioned above are called light ions
compared to much heavier ions such as, for example, uranium [43].
In the following section, heavy ions include ions heavier than protons (and helium
ions). They combine the advantages of an excellent physical selectivity comparable to that of
protons with the radiobiological advantages of high-LET radiations for some types of
tumors (as discussed for fast neutrons in Sec. 4.1.1). However, as carbon ions are, at the
moment, the only type of heavy ions used in therapy, the next section will deal mainly with
carbon ions.
Rationale: The Bragg Peak and High-LET
Four advantages can be identied for heavy ions in cancer therapy.
Figure 17 Proton beam therapy of tumors of the base of skull. Probability of local control in
patients with chordomas (n = 169) and low-grade chondrosarcomas (n = 165). (From Ref. 39.)
Bragg Peak and Physical Selectivity. The physical selectivity of carbon ions, other
heavy ions, and protons is quite similar. Fig. 19 shows the Bragg peak for carbon ions as a
function of depth [44]. The Bragg peak has to be spread out, as for protons, to fully cover the
planning target volume (PTV). The ratio between the dose at the level of spread-out Bragg
peak (SOBP) and of the initial plateau is compared for carbon ions and protons and for
dierent ions in Figs. 20 and 21 [44,45].
Nuclear fragmentation observed with carbon and other heavy ions could be a
disadvantage as some energy is deposited beyond the primary Bragg peak. This issue is
probably not clinically relevant as the involved absorbed dose level is lowand the fragments
are low-LET particles. The penumbra is somewhat narrower with carbon ions than with
protons as the particles are heavier.
High LET and RBE. More important is the fact that the LETthus also the RBE
increases with depth in the hadron beam (Figs. 22 and 23) [43]. This further increases the
Figure 19 Bragg curves for carbon beams with dierent energies. When increasing the energy, the
range of the particles increases and the Bragg peak occurs at larger depths. Concurrently, the height
of the Bragg peak decreases. (From Ref. 44.)
Figure 18 Comparison of photon and proton dose distributions for the treatment of a cra-
niopharyngioma in a child. Typical planning sections for a large suprasellar craniopharyngioma, in a
3-year-old child, treated with photons (A) or protons (B). The planning target volume (PTV) is
indicated by the hatched area. For photons and protons, four equally weighted beams are used and
the normalization point was chosen at the intersection of the beam axes. For the four proton beams,
the Bragg peak was spread over 4 cm. (From Ref. 41.)
ratio of the biological equivalent doses between the SOBP and the initial plateau (Fig. 24)
[44]. The clinical benet of a higher RBE at the level of the distal part of the SOBP is
illustrated in Fig. 25 [45].
High-LET Advantage. Thirdly, high-LET irradiation is delivered at the level of the
SOBP where the PTV(thus the cancer cell population) is located. Heavy-ion beams are thus
specically eective against some tumor types as discussed for fast neutrons (see Secs. 4.1.1
and 4.1.3).
Repair Capacity. Finally, when fractionated treatment is applied, the high-LET
radiation at the level of the SOBP (i.e., PTV) partly prevents or reduces cell repair. In
contrast, the normal tissues irradiated at the level of the initial plateau are exposed to
Figure 20 Comparison of calculated extended Bragg peaks of protons and carbon ions (
12
C) at
dierent penetration depths. (From Ref. 45.)
Figure 21 Comparison of the biological dose proles for He, C, and Ne ions. For carbon ions,
the ratio of the biological dose at the level of the SOBP and in the initial plateau is maximized and
the fragmentation tail behind the Bragg peak remains relatively low. These arguments lead to select
carbon ions as most appropriate for heavy-ion beam therapy. (From Ref. 44.)
Figure 22 Comparison of interactions of 1-MeV protons and 1 MeV/u C
6+
ions with water. (From
Ref. 43.)
low(er)-LET radiation and can thus fully benet from repair mechanisms if fractionated
irradiation is used.
Technological AspectsBeam Delivery
The technical problems related to beam delivery are, to some extent, similar to those
encountered with protons [46]. They are, however, more complex with carbon (heavier) ions
and involve more cumbersome and more expensive equipment.
The scanning beam allows a better shaping of the treated volume. This is especially
important when the PTVis close to a critical normal structure. This advantage holds for any
shape of the PTV. The principle of the scanning beam technique is presented in Fig. 26 [45].
A rotating isocentric gantry is, or will be, installed in many of the carbon therapy
facilities. The possibility of orientating the beam in any suitable direction is obviously an
advantage for accurate patient-beam positioning and for allowing the selection of the
optimum treatment plan. Isocentric gantries are used in all modern photon linear accel-
erators. For making any comparison relevant and reliable, it is thus important that carbon-
ion therapy could be delivered with the same geometrical possibilities and with the same
accuracy as the classical photon treatments. Mounting an isocentric gantry for carbon-ion
therapy raises complex mechanical problems and requires huge and expensive magnets (Fig.
27) [43].
Clinical Results (Short Survey)
The Berkeley Program. The rst heavy-ion therapy program was initiated at
Berkeley, and 433 patients were treated between 1975 and 1992 [47]. The program was
limited by the availability of the machine and its complexity (which resulted in many un-
scheduled down times), and, as a consequence, there was a patient recruitment problem.
Figure 23 Variation of RBE as a function of depth in the carbon-ion beam used for clinical
applications at HIMAC, Chiba, Japan (carbon-12, 290 MeV/u, SOBP 60 mm). The biological system
is the well-codied intestinal crypt regeneration in mice. The selected criterion is 20 regenerating
crypts per circumference after a single fraction irradiation. RBE determinations were performed at
the beginning, middle, and end of the SOBP and at the level of the initial plateau. The doseeect
relationship for cobalt-60 is indicated for comparison. An estimation of the LET is presented for
each depth where biological determinations were made. (From Gueulette, unpublished.)
Nevertheless, a great deal of valuable radiobiological and clinical information was obtained
(Table 6).
A summary of the clinical results obtained with neon ions in Berkeley is presented in
Table 7 [4,47]. Some fast neutron therapy results are also presented. Although the recruit-
ments are not comparable, it should be pointed out that tumor types or sites for which an
advantage was found with neon ions are those for which an advantage was also found with
fast neutrons. This suggests a specic high-LET eect.
Figure 24 (a) Comparison of the physical and biological depthdose curves for a carbon beam
with a 10-cm SOBP. The biological dose is obtained by multiplying, at each depth, the absorbed dose
by a weighting factor W
RBE
which takes into account the RBE increase. The highest RBE is obtained
in the deepest part of the PTV where the dose is delivered by a single Bragg peak (thus with high
LET and RBE). In contrast, the dose in the proximal part of the PTV is due to many initial-
plateau contributions (thus with a lower LET and RBE). (b) In order to cover the whole PTV with a
homogeneous biological dose, the shape of the physical dose has to be adapted taking into account the
RBE variation over the PTV. (From Ref. 44.)
Figure 25 Treatment of a tumor of the base of skull with a carbon-ion beam. Comparison of the
(physical) absorbed dose and of the biological dose (i.e., the dose weighted for the RBE variation
in the carbon beam). The treatment is carefully planned in order to obtain a homogeneous biological
dose to the PTV. For the same biological dose to the PTV, the normal tissues in the initial plateau
receive a lower dose. (From Ref. 45.)
Figure 26 Principle of the irradiation of a PTV of any shape using the scanning-beam technique.
The PTV is stratied into a series of layers, perpendicular to the incident beam. The dierent layers
are irradiated successively with narrow pencil beams of equal range, scanned over the surface
(dierent shape at each depth) by two deecting magnets. (From Ref. 45.)
The HIMAC-NIRS Program. After the shutdown of the therapy facility at Berkeley,
the National Institute for Radiological Sciences (NIRS) in Chiba, Japan initiated a therapy
program with carbon ions. In 1993, construction and installation of the Heavy Ion Medical
Accelerator in Chiba (HIMAC) was completed. This was the worlds rst carbon-ion
accelerator fully dedicated to medical use in a hospital environment. The HIMAC project
was part of the Japanese governments 10-year plan against cancer.
There was no limitation on machine time, and it was thus possible to study common
tumors on a large scale. A total number of 1297 patients were treated between 1994 and
August 2002.
Some of the clinical results are summarized in Table 8. More detailed information on
lung cancers [nonsmall cell lung cancer (NSCLC)] is given in Table 9, in particular, about
patient selection and treatment conditions [48]. The possibility of hypofractionation has
been investigated especially for lung and liver cancers with no increase in toxicity.
The clinical experience previously gained in the same center, during the last decades,
with fast neutrons was reported to be useful to identify the patients suitable for high-LET
Figure 27 Isocentric gantry for irradiation of the PTV from any direction. The use of an isocentric
gantry for carbon-ion therapy requires huge and expensive magnets. (From Ref. 43.)
Table 6 Summary of the Clinical Results Obtained with Helium Ions and Neon Ions at Berkeley
Tumor site
Local control rate with
Helium ions Neon ions
Conventional
treatment
Salivary gland 80% (10 patients) 28% (188 patients)
a
Nasopharynx paranasal sinus 53% (13 patients) 63% (21 patients) 21% (97 patients)
(UCSF)
Sarcoma 65% (17 patients) 45% (24 patients) 28%
a
Prostate 100% (9 patients) 6070%
a
Lung 39% (18 patients) 2240% (UCSF)
Brain/glioblastoma
(median survival)
17 months
(13 patients)
912 months (UCSF,
RTOG, NCOG)
a
Literature review.
Source: Ref. 47.
therapy and to select the best weighting factor W
RBE
to take into account the RBE eects
(see Secs. 3.5 and 3.6).
A second medical facility dedicated to cancer treatment has been opened at Hyogo,
Japan in 2001.
The European Experience. In Europe, the rst patients were treated with carbon ions
at the Gesellschaft fu r Schwerionenforschung (GSI), Darmstadt, Germany at the end of
Table 7 Comparison of Some Clinical Results Obtained with Neon Ions and Fast Neutrons
(i.e., External Beam and High-LET Radiation)
Tumor site or type
Local control rates after treatment with
a
Fast neutrons
(pooled data)
Neon ions
(Berkeley)
Salivary gland tumors 67% (24%) 80% (28%)
Paranasal sinuses 67% 63% (21%)
Fixed cervical lymph nodes 69% (55%)
Sarcomas 53% (38%) 45% (28%)
Prostatic adenocarcinoma 77% (31%) 100% (6070%)
a
For comparison, the best estimates of local control rates currently obtained with conventional photon beam
therapy are given in parentheses.
Source: Ref. 2.
Table 8 Results of Carbon-Ion Beam Therapy at NIRS (Treatments: June 1994August 2001)
Protocol Phase Material
Treatment
(fractions/week)
No. of
patients
Response
rate (%)
a
Two-year
local
control (%)
b
Three-year
survival (%)
H&N-1 I/II Locally advanced 18/6 17 73 80 44
H&N-2 I/II Locally advanced 16/4 19 68 71 44
H&N-3 II Locally advanced 16/4 134 52 61 42
Lung-1 I/II Stage I (peripheral) 18/6 47(+1) 54 62 88
Lung-2 I/II Stage I (peripheral) 9/3 34 85 86 65
Lung-3 I/II Stage I (Hillar) 9/3 10 90 100
Lung-4 II Stage I (peripheral) 9/3 50(+1) 65 100 73
Lung-6 I/II Stage I (peripheral) 4/1 18 67
Liver-1 I/II T2
f
4 MONO 15/5 24(+1) 75 79 50
Liver-2 I/II T2
f
4 MONO 4
f
12/1
f
3 82(+4) 72 83 45
Liver-3 II T2
f
4 MONO 4/1 11 55
Prostate-1 I/II B2
f
C C ion+hormone 35 100 94
Prostate-2 I/II A2
f
C C ion+hormone 61 100 97
Prostate-3 II TIC
f
C C ion+hormone 47
Uterus-1 I/II III = Iva(ACC) 24/6 30 100 50 40
Uterus-2 I/II Iib-Iva(SCC) 24/6 14 100 67 36
Uterus-3 I/II Iib-Iva(SCC) 20/5 11 100
Uterus I/II Advanced (Adenoca) 20/5 12 100 38 39
Bone/Soft-1 1/II unresectable 16/4 57(+7) 36 77 50
Bone/Soft-2 II unresectable 16/4 30(+1) 57
a
Response rate: percent of tumors with >50% reduction in size.
b
Local control rate: percent of tumors with no evidence of local recurrence or relapse.
Source: Ref. 48.
1997. Because of the strict limitation in the availability of the machine time, patients with
dicult tumor localizations were selected. For these patients, full advantage could be taken
from the scanning beam and the energy modulation system [45].
At the end of 2002, 156 patients were treated, a large proportion of themfor a tumor of
the base of skull. At the end of 2001, for chondrosarcomas (23 pts), no local recurrence was
observed, while, for chordomas (44 pts), the local control rate was 87% (Kraft, personal
communication). The same dierence in prognosis between the two histologies is found as
with protons (Sec. 4.2.2).
Taking into account the clinical experience reported fromBerkeley and Chiba and the
clinical results of the pilot study at the GSI in Darmstadt, both conrming the radio-
biological and physical arguments in favor of heavy ions, the German Cancer Research
Center decided to build a carbon-ion therapy facility at the University Hospital in
Heidelberg. The technical and medical experience gained at the GSI, mainly by Kraft and
his team, will help to select the optimumconguration. The possibility to treat with protons
at the same facility is also planned: this would allowthe medical teamto evaluate the benet
of high-LET vs. low-LET radiations delivered with the best possible physical selectivity. It
would of course be of great interest to have the possibility to treat either with low- or high-
LET radiations depending on the tumor characteristics and patient conditions, in the same
center, under the same technical conditions and with the same medical team.
Four other hadron-therapy centers are planned in Europe: MED-AUSTRON in
Wiener Neustadt in Austria, Espace de Traitement Oncologique par Ions Le gers dans le
Cadre Europe en (ETOILE), TERAin north of Italy, and the Swedish project in Stockholm.
AEuropean network ENLIGHT has been initiated in 2002 by the European Society
for Therapeutic Radiology and Oncology (ESTRO) and supported by the European Com-
mission (EC). The goal of the European Network on Light Ion Therapy (ENLIGHT) is to
coordinate the ve European programs and, in particular, facilitate the mobility of scientists
and exchange information. The scientic coordination of ENLIGHT is the responsibility of
A. Wambersie (ESTRO-Brussels), J.-P. Ge rard (Lyon), and R. Po tter (Vienna).
4.5. Boron Neutron Capture Therapy
Only a short review of BNCT is presented here. The rationale for BNCT is to reach a
physical selectivity at the cellular level [5,49,50]. BNCT is a bimodal, binary therapy where
Table 9 Results of Carbon-Ion Beam Therapy at NIRS: Clinical Studies for Stage I Nonsmall
Cell Lung Cancer (NSCLC)
Protocol no.
Lung-1
(9303)
Lung-2
(9701)
Lung-3
(9801)
Lung-4
(9802)
Lung-6
(0001)
Phase I/II I/II I/II II I/II
Period of the study Oct. 1994 to
Sep. 1997
Sep. 1997 to
Feb. 1999
Apr. 1998 to
present
Apr. 1999 to
Dec. 2000
Dec. 2000 to
present
Tumor type All type
a
Peripheral Central Peripheral Peripheral
Total Dose (GyE) 59.4
f
95.4 68.4
f
79.2 57.6
f
64.8 72 54 or 60
Fraction/weeks (xed) 18f/6w 9f/3w 9f/3w 9f/3w 4f/1w
# Pats (# Tumors) 47(48) 34(34) 15(15) 50(51) 35(35)
Adenoca/SCC/Large cellca 26/22/0 18/15/1 13/2/0 32/19/0 23/11/1
a
All type includes both peripheral and central type of tumor.
Source: Ref. 48.
an alpha particle is produced at the cellular target by the capture reaction of boron
compounds and thermal/epithermal neutrons.
BNCT using thermal neutron beams was started in the United States in 1951 at the
Massachusetts Institute of Technology (MIT) and at the Brookhaven National Laboratory
(BNL). The clinical results were very poor. The technique was introduced in Japan by
Hatanaka in 1968, and some promising results were obtained.
BNCT was restarted in the United States in September 1994 at Brookhaven National
Laboratory and shortly thereafter at MIT using epithermal neutron beams (BNL trials
ended in 1999 after the treatment of 53 patients but continued at MIT); these programs are
supported by the Department of Energy. Forty patients were treated by the end of 1997. In
Europe, the European Commission supports a BNCT programin Petten, The Netherlands.
The three rst patients were treated in 1997. The thermal neutron beam program continues
in Japan.
So far, the only available sources of epithermal neutrons, with sucient output, are
nuclear reactors. However, construction of compact proton accelerators, producing epi-
thermal neutrons of adequate energy (e.g., 2.5-MeV protons on a lithium target), has been
envisaged.
The main expected advantage is that such an accelerator could be hospital-based, and
thus fractionation (of the irradiation and drug administration) could be optimized since the
machine would be available 24 hr a day. In addition, patient positioning could be made
easier and more accurate.
Lastly, BNCT is used today in combination with fast neutron therapy in some centers
such as Seattle, Essen, and Orle ans. Boron is incorporated in the tumor cells; it captures
thermal neutrons produced in the body by the fast neutron beam. Combination of BNCT
and external photon beam therapy has also been suggested [51].
In conclusion, boron neutron capture therapy (BNCT) is still in an experimental
phase. Although the rationale is particularly attractive (selectivity at the cellular level), it is
dicult to draw conclusions from the available clinical data.
5. SUMMARY AND CONCLUSIONS: PRESENT TRENDS
AND EXPECTATIONS IN RADIATION ONCOLOGY
5.1. Radiation Oncology Over the Past Decades
Historically, the progress in radiation therapy has been linked mainly to technological
developments. The physical selectivity of the irradiations was signicantly increased when
200-kV x-rays were progressively replaced by cobalt-60, betatrons, and linear accelerators.
As a consequence, the clinical results were dramatically improved.
More recent technical developments of the electron linear accelerators are impressive.
The reliability, mechanical stability, beam delivery, and collimation systems of the new
generation of accelerators have reached a high level of quality [52]. These machines now
allow irradiation of nearly any target volume with reduced irradiation of the surrounding
organs at risk (OAR).
This progress in the treatment machines could be fully exploited because of the
dramatic and impressive developments in imaging (such as CT, MRI, and PET). In addition,
our better knowledge of the natural history of cancer helps in selecting the optimum
treatment strategy.
For the future, (at least) three main approaches can be identied for improving the
eectiveness of radiation therapy.
5.2. Optimizing Photon Techniques
Powerful irradiation techniques are now available or under development for photons:
intensity-modulated radiation therapy (IMRT), tomotherapy, gamma knife, cyber-
knife, radiosurgery, etc. These techniques make it possible to irradiate any volume of any
complex shape with minimum irradiation of critical normal structures.
This technical progress has been made possible by:
1. Advances in modern imaging techniques, which have made available complete
and accurate anatomical information, including the location of the dierent
target volumes and organs at risk.
2. Developments in medical physics and dosimetry that provide powerful and fast
3-D treatment planning, including inverse planning, and take into account
heterogeneities. Fast computation is absolutely required for IMRT.
3. Engineering improvements that allow full and reliable control of the machine
and beam delivery system and patient immobilization.
These new techniques are becoming available in more and more hospitals.
However, challenges remain.
If one matches the treated volume (TV) and the planning target volume (PTV) as
closely as possible, the conformity index will approach unity [6,7,53]. Dierent technical
approaches are used to reach this goal; among them is IMRT. However, when optimizing
the treatment parameters to improve the conformity index in IMRT, other indices can
change adversely. For example, the irradiated volume increases (integral dose) and the
homogeneity throughout the PTV may become worse. The compromises to be made vary
with the treatment modality, and the true therapeutic gain of the newer modalities still needs
to be evaluated.
This brings us to an important question: has the ecacy of photon beam therapy now
reached a plateau (at least as far as physical selectivity is concerned)? If this is the case, little
additional clinical benet can be expected from further technical improvements with
photons, and one has to search for other beam or radiation qualities to further improve
the eectiveness of radiation therapy.
This is an important point to consider; however, there is no general consensus as yet.
5.3. Proton Beam Therapy
The introduction of proton beams aims at further improving the physical selectivity of the
irradiation. The clinical results obtained by the pioneers in proton therapy, with machines in
physics laboratories, were suciently convincing to justify building and buying dedicated
hospital-based proton machines.
The challenge for the next few years will be to conrm, on a larger scale, the results of
the pioneers and to conrm that their excellent results were actually due to the protons
themselves and not only to the expertise and the motivation of the teams.
The benet expected from the better physical selectivity of protons will have to be
evaluated in comparison with conventional photon beam therapy, which remains the
reference radiation therapy modality.
When making this comparison, one must remain aware of the modern developments in
photon therapy such as conformal therapy (3DCRT), IMRT, tomotherapy, gamma knife,
stereotactic x-ray techniques, iodine-125 (and palladium-103) seeds and plaques, etc.
There are, however, some (rare) tumor localizations for which nothing can compete
with the excellent physical selectivity of protons: for example, tumors adjacent to the spinal
cord, adjacent or invading the brain stem, tumors of the base of skull, and certain (especially
pediatric) brain tumors (Fig. 18).
Another advantage of protons, relative to the best photon techniques, is a reduction of
the integral dose and of the irradiated volumes. This factor could inuence the risk of radio-
induced cancers, although, so far, epidemiological evidence is still lacking.
Proton therapy equipment is now commercially available from several companies.
This is a sign that protons have gained their place in the radiation therapy arsenal. Indeed,
the number of proton therapy facilities increases worldwide, both the hospital-based,
therapy-dedicated facilities and the facilities in physics laboratories adapted for medical
applications.
5.4. High-LET Radiations, Fast Neutrons, and Hadrons
The third approach is the introduction of another type of radiation quality: high-LET
radiation. Clinical experience with neutrons has demonstrated that high-LETradiations are
superior to low-LETradiations for some tumor types or sites. Fast neutrons were indeed the
rst high-LET radiations to be applied clinically (see Sec. 4.1). Although in the rst studies
they were applied in suboptimal conditions froma technical or dose distributions point of
view, their advantage for some types of tumors is well established, particularly for slowly
growing, well-dierentiated tumors. Randomized trials have indeed shown their superiority
over conventional photons for salivary gland tumors and prostatic adenocarcinomas.
Unfortunately, several neutron therapy centers were closed for technical reasons or
patient recruitment diculties. However, the centers applying neutron therapy today benet
from the same conditions of safety, reliability, and physical selectivity as photon therapy
centers.
Heavy ions combine the benet of the high physical selectivity of proton beams and the
biological advantage of high-LET radiation for some tumor types. They appear today to be
one of the most promising radiation therapy modalities when the clinical indication is
correctly selected (some tumor types and/or localizations).
When comparing the relative merits of the dierent types of radiation used in therapy,
two criteria have to be considered: the physical selectivity and the radiation quality (actually
the LET). They are schematically presented in Fig. 28 [54]. Improving the physical selectivity
is per se always an advantage. In contrast, selection between low and high LET depends on
the tumor characteristics and should be based on the histology, grade, doubling time, etc. It
is a pure radiobiological and medical issue.
Reliable criteria to identify the (individual) patients suitable for high-LET radiation
therapy need to be developed. At present, the available criteria are derived (mainly) fromthe
clinical fast neutron experience. It can be expected that novel approaches based on modern
techniques involving molecular biology or gene identication may provide appropriate and
still missing information. They may also provide information on the susceptibility or risk for
secondary radio-induced cancer.
5.5. Reporting the Treatments
It is important for the future that protocols and results of hadron therapy be reported and
analyzed using the terminology, denitions, concepts, and approaches currently in use for
the other radiation therapy modalities [7,53].
As fractionated photon beamtherapy is the reference radiation therapy modality, used
for more than 80%of the patients, the terminology in use for photons should be applied for
the other techniques. Recommendations for reporting are contained in several ICRU
reports [6,7,53]. It is, however, recognized that each technique has its specicity and may
sometimes require introduction of specic concepts or denitions.
5.6. Global Approach and Collaboration in Cancer Treatment Strategy
The subject of this chapter is to report the rationale, achievements, and expectation of ions in
cancer therapy. To illustrate their potential, the proven advantages of low- and high-LET
ions are discussed in detail.
In the eld of radiation therapy, it is recognized that there are other promising
approaches to improve the eciency of the treatment such as better individual adaptation of
fractionation or association with drugs to modulate the radiation sensitivity. Combination
of radiotherapy with the two other classical methods of cancer treatment, surgery, and
chemotherapy may also be optimized.
Figure 28 Schematic presentation of the relative situation of the dierent types of radiations used
in therapy. Two criteria are considered: the physical selectivity and the LET (or radiobiological
properties). For the low-LET radiations, the physical selectivity was improved from the historical
200-kV x-rays to cobalt-60 gamma rays and the modern linacs. Even with the linacs today, sig-
nicant improvement is continuously achieved (IMRT, etc.). Among the low-LET radiation, the
proton beams have the best physical characteristics, but one of the issues is the proportion of patients
who will benet from proton irradiation. A similar scale can be drawn for high-LET radiation: the
heavy-ion beams have a physical selectivity similar to protons. Selection between low- and high-LET
radiation is a biological/medical problem; it depends on the tumor characteristics, and reliable criteria
still need to be established (see text). (From Ref. 54.)
Last but not the least, the progress in gene therapy, immunotherapy, and other
approaches based on novel molecular biology techniques has to be kept in mind as well.
The recent impressive developments in ion beam therapy should not be regarded as
being in competition with the other approaches mentioned above. In contrast, the
advantages of combinations should be considered and a potential enhancement of the
respective eectiveness may reasonably be expected [5].
ACKNOWLEDGMENT
This work was supported by the European Commission, Directorate General Research-
Quality of Life and Management of Living Resources, contract: QLGI-CT-2002-01574.
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26
Food Irradiation
Jo zsef Farkas
Szent Istvan University, Budapest, Hungary
1. INTRODUCTION
Food irradiation is the process of exposing food, either prepackaged or in bulk, to
controlled levels of certain types of ionizing radiation to increase storage life of food,
reduce postharvest food losses, and inactivate specic food-borne pathogenic organisms.
Food irradiation is one of the most thoroughly and intensively investigated methods of
food preservation.
The ionizing radiation applied in food irradiation is limited to high-energy electro-
magnetic radiation (gamma rays or x-rays) with energies up to 5 MeV or high-energy
accelerated electrons with energies up to 10 MeV. These radiations are chosen because
1. They produce the desired eects with respect to the food.
2. They do not induce radioactivity in foods or their packaging materials.
3. They are available in quantities and at costs that allow practical uses of the
process.
Other kinds of ionizing radiation, in some respect, do not suit the requirements of
food irradiation. Except for dierence in penetrability, electromagnetic ionizing radiations
and accelerated electrons are equivalent in food irradiation and can be interchangeably
used.
Radiation treatment can be considered as one type of nonthermal processing of
food because even at the largest absorbed radiation dose (see Sec. 4.11) to be applied,
which is about 50 kGy, the amount of energy is equivalent to 50 J. At this dose level, if all
the absorbed radiation energy would be degraded to heat, the temperature of a high-
moisture food, thermodynamically roughly equivalent to water, would rise about 12jC.
Because of the negligible heating eect, irradiation treatment is able, e.g., to kill the cells of
microbes contaminating frozen foods without thawing them up, or, those in fresh
commodities without changing the original physical state of the product.
Irradiation can be applied through any packaging materials including those that
cannot withstand heat. This also means that radiation treatment can be performed after
packaging, thus avoiding recontamination or reinfestation of the product.
The useful eects of ionizing radiation as a food processing means are summarized in
Table 1. In addition to the preservative eects listed in Table 1, in some cases even
improvement of certain functional or sensory quality characteristics of food can be
achieved with irradiation.
The basic process is the application of a prescribed amount of ionizing radiation to
foods, plus the eventual use of certain other procedures that may be needed to accomplish
the purpose of the processing.
Food irradiation is a very complex topic and has an enormous literature. Apart from
thousands of journal articles and proceedings of large number of international conferences
and panel meetings, its state of the art has been extensively reviewed during the course of
decades by a number of noteworthy books [15]. The present brief chapter mainly focuses
on the principles and some potential applications of food irradiation and refers to some
most recent research and developments in these regards.
1.1. Principles of Radiation Sources
Two basic types of radiation sources can satisfy the requirement of industrial use of food
irradiation:
1. Machine sources such as electron accelerators and those converting acceler-
ated electron beams to x-ray photons. Accelerated electrons have low penetra-
bility. Thus they cannot meet all the goals of food irradiation. The 10 MeV elec-
trons, the highest energy level of electron irradiation presently recommended
by the Codex Alimentarius [6], can penetrate food with typically about 4-cm
thickness.
2. Long half-life, man-made radionuclides emitting gamma rays. The most readily
available is cobalt-60. Much more limited is the use of cesium-137. Gamma rays
and x-rays have highly penetrating characteristics; thus, they can be used to treat
food in large containers.
Typical irradiation facilities consist of a process chamber containing the radiation
source, some sort of conveyor systems to transport products inside and outside the
shielding walls, and sophisticated control and safety systems. Irradiation facilities are built
with several layers of redundant protection to detect equipment malfunctions and protect
employees from accidental exposure. Technical details depend on the type of irradiation.
Typical processing parameters are compared in Table 2 [7].
Table 1 Useful Eects of Irradiation as a Food Processing Treatment
Eects Results
Inhibition of sprouting of tubers
and bulbs
Increased storability
Decrease of after-ripening and delaying
senescence of some fruits and vegetables
Increased shelf life
Killing or sterilizing stored
product insects
Insect disinfestation of food
Inactivation of parasites transmissible
by food
Prevention of food-borne
parasitic diseases
Inactivation of food-borne
microorganisms
Microbial decontamination of food: Increased
shelf life and/or prevention of food poisoning
1.2. Typical Dose Requirements
The technological feasibility of a food irradiation treatment depends on how much
irradiation the food withstands without adversely changing its qualities, i.e., how much
useful eect can be achieved without signicant change to the chemical composition,
nutritional value, and sensory properties of the product. Generally, there is a minimum
dose requirement. Whether every mass element of a food requires irradiation will depend
Table 2 Comparison of Typical Processing Parameters
Gamma X-ray E-beam
Typical source
power
3.5 MCi 25 kW 35 kW
Typical processing
speed
12 tonnes/
hr at 4 kGy
10 tonnes/
hr at 4 kGy
10 tonnes/
hr at 4 kGy
Source energy 1.33 MeV 5 MeV 510 MeV
Penetration depth 80100 cm 80100 cm 810 cm
Dose homogeneity High High Low
Dose rate Low High Higher
Best application Bulk processing of large
boxes or palletized
product in shipping
cartons in a warehouse
environment
Bulk processing large
boxes or palletized
product in shipping
cartons in a warehouse
environment
Sequential processing of
primary or secondary
packaged product
in-line or at-line
Source: Ref. 7.
Table 3 Dose Requirements of Various Applications
of Food Irradiation
Application Dose Requirement (kGy)
Inhibition of sprouting of
potatoes and onions
0.030.12
Insect disinfestation of seed
products, ours, fresh and
dried fruits, etc.
0.20.8
Parasite disinfestation of
meat and other foods
0.13.0
Radurization of perishable
food items (fruits, vegetables,
meat, poultry, sh)
0.510
Radicidation of frozen meat,
poultry, eggs and other
foods and feeds
3.010
Reduction or elimination of
microbial population in dry
food ingredients (spices, starch,
enzyme preparations, etc.)
3.010
Radappertization of meat, poultry,
and shery products
2560
on the purpose of the treatment. In some cases, irradiation of the surface will suce; in
others, the entire food must receive the minimum dose.
Ranges of dose requirement of various applications are listed in Table 3. The details
of the requirements for each food must be specically considered.
2. BIOLOGICAL EFFECTS OF IONIZING RADIATION
Chemical and biological eects of ionizing radiation are thought to occur through two
main mechanisms: direct interaction of the radiation with food components and living
cells in materials exposed to it, and indirect action from radiolytic products, such as the
radicals formed from water molecules (see Chap. 12).
The primary target of biological eects appears to be the DNA (see Chap. 15),
although eect on the cytoplasmic membrane may also play a role [8]. Ionizing radiation
aects DNA in a number of ways. It causes chemical changes in specic nucleotide bases;
it causes single-strand breaks; and it causes double-strand breaks in a dose-dependent
manner.
2.1. Radiation Sensitivity of Stored Product Insects and Food-Borne
Parasites
The radiation dose required to kill an insect depends on the species and a number of other
factors such as age, sex, and stage of development [9]. In general, radiation sensitivity is
highest at the egg stage and the lowest at the adult stage of development. Fruit ies are the
most radiation-sensitive insect pests while the moths are the most resistant ones.
Radiation eects on parasitic protozoa and helminths are associated with loss of
infectivity, loss of pathogenicity, interruption or prevention of completion of life cycle,
and death of parasites [10].
2.2. Radiation Resistance of Food-Borne Microorganisms
The actual number of cells or percentage of microbial population that will be killed by an
absorbed radiation dose depends also on various factors such as the inherent resistance of
the particular organism, the growth stage, as well as environmental factors such as tem-
Table 4 D
10
Values (kGy) of Some Nonsporeforming Bacteria
Bacteria Nonfrozen Food Frozen Food
Vibrio spp. 0.020.14 0.040.44
Yersinia enterocolitica 0.040.21 0.200.39
Campylobacter jejuni 0.080.20 0.180.32
Aeromonas hydrophila 0.110.19 0.210.34
Shigella spp. 0.220.40 0.220.41
Escherichia coli (incl. O157:H7) 0.240.43 0.300.98
Staphylococcus aureus 0.260.57 0.290.45
Salmonella spp. 0.180.92 0.371.28
Listeria monocytogenes 0.201.0 0.521.4
perature during irradiation, oxygen presence, and water content. Vegetative cells of path-
ogenic bacteria, the main concern in many food-borne infections and intoxication, are
relatively radiation sensitive, including both long-time recognized pathogens as well as
emerging or new ones.
Table 4 shows the ranges of decimal reduction doses (D
10
values) of the most
important nonsporeforming pathogens determined in various atmospheres and foods,
summarized from publications by a large number of laboratories [11,12]. Because of the
eect of irradiation temperature on the radiation resistance of microorganisms, a detailed
knowledge of product temperature prole is critical for eective ionizing radiation
pasteurization of foods, particularly meat products [12,13]. Some nonpathogenic micro-
organisms and the bacterial spores in general are more resistant to radiation than those
listed in Table 4. Viruses, mycotoxins produced by certain types of molds, and prion
particles thought to be responsible for bovine spongiform encephalpathy (BSE) in cattle
are highly resistant to irradiation [11].
3. RADIATION-INDUCED CHEMICAL CHANGES IN MAIN CONSTITUENTS
OF FOODS
More or less, water is present in almost all foods. Therefore the radiolysis of water is of
particular interest in food irradiation. However, this subject is amply dealt with in Chap.
12. The end products of water radiolysis,
.
OH, e
aq
, and
.
H, are very reactive transient
species. The hydroxyl radical is a powerful oxidizing agent whereas the hydrated electron
is a strong reducing agent. The stable end-products such as hydrogen and hydrogen
peroxide are of less signicance because they are largely consumed with their respective
reactions with e
aq
and
.
OH [14].
The presence or absence of oxygen during irradiation can have an important
inuence on the course of radiation-induced changes of food components. When foods
are irradiated, oxygen can add to some of the radicals produced to form peroxy radicals,
.
RO
2
. Through this reaction, the small amount of oxygen normally present in a food can
be quickly consumed during irradiation. Because diusion of oxygen from the atmosphere
is slow, electron irradiation, due to its high dose rate, can create an anoxic condition in the
food, whereas gamma sources have much lower dose rates than electron accelerators. Thus
anoxic conditions are not necessarily created unless the food is gamma irradiated in an
oxygen-free package. This might create a dose rate eect that is actually an oxygen eect.
The radiolysis of water is pH-dependent, too. Thus pH inuences the result of a radiation
treatment.
The temperature during irradiation also inuences the chemical changes. Freezing
can have a strong protective eect because reactive intermediates of water radiolysis are
trapped in the ice of frozen foods and are thus kept from reacting with other food
components. During thawing of frozen, irradiated food, the radiolytic products of water
apparently react preferentially with each other rather than with other food components.
Thus freezing of food has a certain protective eect on some radiation-sensitive vitamins
[15] and decreases the associated chemical changes, e.g., with the formation of volatiles
producing o-avor in some irradiated foods [16].
Because in multicomponent systems such as foodstus, a mutual protection of
dierent components is exerted, irradiation does not cause much chemical change in
foods.
Minerals and trace elements cannot be aected under the process conditions of food
irradiation.
3.1. Effects on Main Organic Components
Apart from water, the major constituents of most foods are carbohydrates, proteins, and
lipids. These organic components of foods are less sensitive to irradiation than they are in
their pure solutions as a single-component system.
Irradiation of sugars results in the formation of low levels of radiolytic products
mostly derived from the reaction with hydroxyl radicals by hydrogen abstraction from the
CH bonds, resulting in products such as sugar acids, keto sugars, and deoxy compounds
[17]. When polysaccharides are irradiated, the reactions observed with monosaccharides
can occur, and, additionally, the glycosidic bonds that connect the monosaccharide units
can be broken. This reduces the degree of polymerization. Especially in case of starch and
pectin, this causes changes in the physical properties of the foods that contain them.
Changes in properties such as viscosity, mechanical strength, swelling, and solubility are
likely to reduce their functionality in food; however, sometimes, the changes improve a
particular function.
Major in vitro reactions of irradiated amino acids involve decarboxylation and
oxidative (if oxygen is present) or reductive (if anoxia exists) deamination [14]. The
sulfur amino acids such as cysteine, cystine, and methionine may act as free radical scav-
engers, thus ameliorating the degradative eects on other components of food. However,
their breakdown also generates end products such as hydrogen sulde, which has
undesirable sensory eects. Radiation damage to constituent amino acids in irradiated
food is very limited. With some 20 amino acids, the total range of possible reaction
products is great, but the quantitative eect on proteins in foods during irradiation is
small. Consequently, enzyme inactivation is also insignicant. Actually, radiation-
sterilized foods destined for long-term storage must receive a heat treatment (blanching)
in addition to the radiation treatment to prevent enzymatic spoilage (see Sec. 4.11). In
some irradiated plant tissues, the in vivo enzyme activities may increase as a result of
release, or diusion, through leaky membranes more easily reaching their hitherto
unavailable substrates. When meat is irradiated at high doses (1050 kGy), radiation-
induced aggregation of some proteins may occur, which leads to decreased protein
solubility [14].
Upon irradiation of fats, the formation of a multitude of products is possible af-
ter primary ionization and excitation, and deprotonation followed by various dimer-
ization, disproportionation reactions, dissociations, or decarboxylation. It is generally
assumed that irradiation in the presence of oxygen leads to accelerated autooxidation
of lipids, and that the pathways are the same as in light-induced or metal-catalyzed
autooxidation.
The irradiation of unsaturated fatty acids in foods predominantly results in the
formation of a hydroperoxyl radical and then the formation of a hydroperoxide. The
hydroperoxides are generally unstable in foods and break down to form mainly carbonyl
compounds, many of which have low odor threshold, and contribute to the rancid notes
often detected when fat-rich foods are irradiated [18]. In the absence of air, their formation
is limited.
In studies on radiation eects on cholesterol in meat [19] and egg powder [20],
elevated levels of the same oxides were found that are known to result from
autooxidation during storage of unirradiated foods. Vacuum packaging or addition
of antioxidants can largely prevent such formation of cholesterol oxidation products
[21,22].
Radiation eects on vitamins will be discussed in Sec. 5.
4. PRACTICAL APPLICATIONS OF FOOD IRRADIATION
4.1. Control of Sprouting and Germination of Vegetable Crops
Inhibition of sprouting of various vegetable crops at low doses was one of the earliest
extensively studied application possibility of food irradiation. Most important from these
opportunities is the control of sprouting to extend the storability of tubers and bulbs [23].
These studies included the response of varieties/cultivars to radiation treatment, optimal
dose, dose-rate eect, time interval between harvest and irradiation treatment for ecacy,
susceptibility of irradiated batches to storage rots, biochemical mechanisms underlying
sprout inhibition, inuence of storage conditions, and the eect of irradiation on
technological properties inuencing the utilization of irradiated crops for processed
products.
The dose required to inhibit sprouting of onions, shallots, and garlics is 0.030.12 kGy.
For good sprout control of tubers such as potatoes and yams, somewhat higher doses, 0.08
0.14 kGy, are required. Because of decreased wound-healing ability after irradiation, doses
in excess of 0.150.2 kGy may induce increased microbial rot in storage [24].
An important factor determining the ecacy of radiation treatment of tubers and
bulbs is the time delay between harvest and irradiation. The sprout inhibition is most
pronounced if the irradiation of tubers and bulbs is applied shortly after harvest, when they
are still in their dormancy stage. However, the dormancy period may vary among cultivars
and cropping season, and is also dependent on the postharvest storage temperature.
In onion bulbs, if some growth of inner buds takes place already before irradiation,
the treatment causes the death and discoloration of the inner buds. The area of this
discoloration depends on the size of the inner buds at the time of irradiation. Pilot scale
studies in Hungary have shown that the yield of unirradiated onions prepared for drying
after storage was 29% of the original compared to 55% in irradiated onions. The
dehydrated onions prepared from irradiated bulbs had better quality than did the controls.
No discoloration of the inner buds occurred in bulbs of cultivar Also go di irradiated at
0.05 kGy and stored up to 8 months [25]. Similar results were reported earlier from Egypt
[26] whereas some studies in the United States have indicated that inner-bud discoloration
of irradiated onions may lower the quality of dehydrated onion slices or powder prepared
from them [27].
In irradiated potatoes, especially in some varieties and as a function of cultivating
conditions of the raw material, after-cooking darkening may occur. This discoloration is
attributed to formation of ferric-phenolic complexes. This phenomenon depends on the
iron content, and is related to increased polyphenol formation and reduced citric acid
levels, which are inuenced by agronomic and climatic factors. Various technological
measures have been developed to prevent this after-cooking darkening [23].
Other types of radiation-induced discoloration in potatoes have also been reported
in some cases and measures to avoid them have been studied [28,29].
Because irradiation interferes with the natural wound-healing process, it is an
important prerequisite of successful application of irradiation that mature tubers with
fully developed periderm are suitable for radiation processing and tubers must be properly
cured from harvesting and handling injuries before irradiation.
Because potatoes are good source of vitamin C, it is important to point out that
irradiation does not adversely aect the vitamin C levels [23,30]. Although some ascorbic
acid is converted into dehydroascorbic acid on irradiation, the latter is also biologically
active.
In Japan, where the use of chemical sprout suppressants is not permitted, commer-
cial irradiation of potatoes has been introduced in 1973 in Shihoro, Hokkaido, where an
industrial scale irradiator has been processing about 15,00020,000 tons of potatoes
annually [31,32]. The success of this system is due in large measure to careful handling
of the product before and after treatment.
Since the late 1990s, commercial irradiation of bulb crops, particularly garlic, has
shown a steady increase using
60
Co irradiators in the major garlic-producing provinces of
China [23].
A commercial demonstration facility for irradiation of onions having a processing
capacity of 10 tons/hr was reported in 1999 to be under construction in Nasik District,
Maharashtra State, India [23].
Pilot-scale irradiation and consumer acceptance studies with tubers and bulbs have
been performed with positive results already in the 1970s in a number of other countries,
e.g., Argentina, Bangladesh, Chile, German Democratic Republic, Hungary, Israel, the
Philippines, Thailand, and Uruguay, showing the techno-economic feasibility of irradi-
ation of these crops. However, in countries under temperate climates, cool storage by
circulating cold outside air, together with the use of chemical sprout inhibitors, provide
inexpensive and satisfactory sprout control with reasonably good product quality for both
industrial processing and household consumption. Thus industrial interest in commercial
implementation in Western countries for sprout inhibition is still very low, basically
because it involves high capital investment for relatively low-price crops, perceived
consumer opposition to irradiated foods, regulation and trade limitations, and labeling
requirements. However, the use of chemicals is coming under increasing scrutiny from the
viewpoints of environmental pollution and health risk from residues left in the products.
Therefore it is likely that their continued use will be restricted.
In yams, an important crop in tropical climates, neither chemical sprout inhibitors
nor cool storage are eective for long-term storage. On the other hand, irradiation would
provide an eective alternative for postharvest treatment.
Controlling the germination of malting barley is an interesting potential application
of low-dose irradiation. Doses of 0.250.5 kGy applied to air-dried barley do not prevent
the emergence of shoot tips and tendrils during malting but markedly retard the root
growth. In this way, high-quality malt can be obtained while the losses resulting from root
growth are reduced [33]. Because this eect of radiation processing persist for at least 7
months, the above radiation treatment applied before the barley is put into storage has the
added benet of destroying insect pests that may be present in the grain.
4.2. Insect Control in Stored Foods
Radiation disinfestation of stored food oers a viable alternative to chemical disinfestation
without adverse eects on the product quality. The use of methyl bromide, the only broad-
spectrum fumigant used for the disinfestation of stored products, was anticipated to be
phased out by around 2001 [34], which highlights the urgency of an alternative treatment.
Disinfestation of stored food by irradiation was extensively studied already in the
1960s and 1970s [9,35], and it has shown that radiation disinfestation can be eciently
applied to almost all dried foods.
The Codex Alimentarius Commission recommends a dose of 1 kGy for killing insects
in all food and agricultural products [6]. However, if Good Manufacturing Practices
(GMP) and Good Irradiation Practices (GIP) are followed, according to subsequent
recommendations published by the International Consultative Group on Food Irradiation
(ICGFI), radiation disinfestation of stored product commodities should be achievable at
doses up to 0.5 kGy [34]. The radiation doses used to control various stored product
insects are summarized in Table 5.
Presently, many commodities have to be fumigated more than once to control
insects. Irradiation by a single treatment sterilizes or kill, depending on the dose and the
time interval allowed after irradiation, all developmental stages of the common insect
pests, including eggs deposited inside grains or even the weevil that may lodge deep inside
the seed of the mango.
With the availability of inexpensive, convenient, and easily applied pest control
methods based on application of pesticides, irradiation disinfestation has not yet received
priority. Nevertheless, radiation disinfestation was performed on an industrial scale in the
Table 5 Radiation Doses Used to Control Stored Product Insects
Species Stage Dose (kGy)
Coleoptera
Sitophilus oryzae All 0.16
S. granarius All 0.16
S. zeamais All 0.16
Tribolium castaneum All 0.20
T. confusum All 0.20
T. destructor All 0.20
T. madeus All 0.20
Rhyzopertha dominica Larvae 0.25
Latheticus oryzae Adults 0.20
Oryzaephilus surinamensis All 0.20
O. mercator All 0.20
Callosobruchus analis All 0.20
C. chinensis All 0.20
C. maculatus All 0.20
Bruchus rumanus All 0.40
Bruchidius incarnatus All 0.40
Trogoderma granarium All 0.25
Dermestes maculatus All 0.50
Lasioderma serricorne All 0.50
Nerobia rupes All 0.30
Araecerus faciculatus All 0.75
Lepidoptera
Anagastus kuehniella Larvae, pupae 0.60
Plodia interpunctella Larvae 0.45
Cadra cautella Larvae, pupae 0.45
Sitotroga cerealella All 0.60
Nemapogon granellus All 0.60
Source: Ref. 34.
Soviet Union, where an electron irradiation plant to treat imported grains went into
operation in 1980 at Port Odessa and some 400,000 tonnes/year of grain were successfully
treated by two electron accelerators. This facility is not currently in use in the Ukraine,
after the collapse of the Soviet Union.
The doses applied for the widely used microbial decontamination by irradiation of
spices, dried herbs, and dry vegetable seasonings (see Sec. 4.9) are much higher than the
disinfestation doses. Thus radiation decontamination of these commodities is more than
enough to kill also any insects eventually infesting them.
Dried fruits, vegetables, and nuts, as well as dried sh, an important source of
protein in many developing countries, are also good candidates for radiation disinfesta-
tion. Application of 0.20.7 kGy doses, if they have been suitably packaged to prevent
reinfestation, can eliminate the insect problem from these products that cannot be
eectively disinfested by either chemical or physical means other than irradiation.
As a residue-free physical treatment, irradiation does not provide any protection
from insects that might reinfest the product after postirradiation storage. Therefore it is of
paramount importance that proper care is needed to store, transport, and market
irradiated products in insect-proof containers or packages [34].
4.3. Irradiation as a Quarantine Treatment
Radiation treatment can signicantly contribute to the variety of means for quarantine
disinfestation in the international trade to prevent the importation of invasive nonnative
insects with food and agricultural commodities that can harbor them. The use of
irradiation disinfestation in quarantine treatment has great potential especially against
fruit ies. A number of past quarantine treatments have been recently prohibited, e.g.,
fumigation with ethylene dibromide.
Irradiation is the fastest among quarantine treatments available, although it cannot
be used to treat so large loads at once as can be carried out with fumigation or by cold
storage. Irradiation treatment is an eective alternative for many types of fresh produce
because it can be used on riper fruit and on fruit that cannot tolerate, e.g., heat treatment.
However, one characteristic of irradiation quarantine treatment that needs specic con-
sideration by regulatory/inspecting agencies is that irradiation does not provide signicant
acute mortality (within 48 h) at doses tolerated by fresh agricultural produce; thus
identication methods for irradiated commodities and insects, or acceptance of certi-
cation as proof of adequate irradiation, are needed [36].
Quarantine treatment doses of several pests (mainly fruit ies) supported by adequate
research vary between 0.07 and 0.225 kGy [36]. Such low doses are tolerated by most fruits.
However, because of the diculties in evaluating ecacy by acute mortality and uncer-
tainties of dose measurements, radiation quarantine treatment research shows some
inconsistencies, and thus further work is required. Nevertheless, motivated by banning
fumigation with ethylene dibromide (EDB), several semicommercial trial shipments of
tropical fruits have been irradiated and marketed in the continental United States since
1986, and a commercial linear accelerator e-beam/converted x-ray facility was built in
Hawaii to treat fruit and began operating in August 2000 [36].
4.4. Parasite Disinfection
Various animal parasites are associated with certain raw and partially processed food, not
only in the developing part of the world but also in developed countries. In the United
States, a recent survey by the Centers for Disease Control and Prevention estimated that
there are 2.5 million cases annually due to food- and beverage-borne parasites [37].
There are a number of traditional and new control measures to protect consumers
from food-borne parasites. Ionizing radiation is one of the new technologies to control or
limit the impact of a number of food-borne parasites on public health [10].
Although relatively high doses (46 kGy) are required to kill food-borne parasites,
much lower doses are adequate to prevent their reproduction and maturation resulting in
loss of infectivity. Table 6 summarizes the eect of ionizing radiation on the most
important parasites that may be associated with shery products and meats [38]. Thus
the parasitic roundworm Trichinella spiralis, which causes trichinosis, the pork and beef
tapeworms, the protozoon in pork responsible for toxoplasmois, and various ukes that
infest sh, can be rendered noninfective by low-dose radiation treatment. Doses of
Table 6 The Eect of Irradiation on Parasites
Parasite Mode of Infection Dose (kGy) Eect of Irradiation
Clonorchis spp. Chinese liver uke, occurs
in raw sh
0.15 In vitro minimum
eective dose
Opistorchis viverrini Liver uke found in
contaminated raw,
pickled or smoked sh
eective dose
Paragonimus spp. Parasitic worm found
in crabs and
craysh in Asia
eective dose
Gnathostoma
spinigerum
Parasitic worm found in
raw, undercooked
or fermented sh
7 Reduces worm recovery
rate in mice
Angiostrongylus
cantonensis
Parasitic worm found in
uncooked molluscs, shellsh
2 Minimum eective dose
Anisakis spp. Nematode is ingested if
sh is eaten raw or
slightly salted
210 Reduces infectivity
of larvae
Trichinella spiralis Nematode occurs in raw or
inadequately cooked pork
0.3 Minimum eective dose
031 FDA permitted dose
to control trichina
in pork
Toxoplasma gondii Consumption of
undercooked
meat or poultry;
or contact with
infected animals
0.7 Minimum eective
dose for
fresh pork
Cysticercus bovis
(Taenia saginata,
in man)
Tapeworm found
in uncooked
or undercooked beef;
causes taeniasis
0.3 Preliminary minimum
eective dose
Cysticercus cellulosae
(Taenia solium,
in man)
Tapeworm found in pork 0.3 Preliminary minimum
eective dose
Source: Ref. 38.
irradiation applied to reduce microbial load (to be discussed in further chapters) are
suciently high to control also many parasites.
4.5. Extension of Shelf Life of Fresh Fruits and Vegetables
Both ripening and reducing fungal decay in many species of harvested fruits and vege-
tables have been studied in relation to food irradiation alone or in combination with other
treatments [39].
Appreciable delay of ripening and consequent enhancement of shelf life have been
noted in some tropical fruits such as bananas, plantain, and mangoes after low-dose
irradiation (0.20.7 kGy) [40,41]. Maximum delay of ripening has been observed with
fruits of lower maturity. However, these feasible levels of doses are close to those that
induce phytotoxicity, and many factors (varietal dierences, the fruits stage of maturity at
the time of irradiation, etc.) make the outcome of the treatment uncertain.
More promising is the delay of maturation in cultivated mushroom (Agaricus sp.)
where a dose of 12 kGy when applied soon after picking at the closed button stage can
extend the shelf life by oppressing cap opening and stalk elongation. At optimal doses,
darkening of the gills, cap and stalk, shriveling, and surface mold development are also
inhibited [42,43].
The feasibility of irradiation of temperate fruits, particularly pome and stone fruits, is
generally limited by adverse eects of texture (softening of the tissue) due to the radiation
sensitivity of pectin. Among temperate fruits, strawberries seem to be the most amenable
to radiation processing, which extends the market life of this perishable fruit by control-
ling molds that otherwise quickly cause decay, particularly Botrytis and Rhizopus rots. The
dose requirement for this decay control is 1.52 kGy, with an upper limit of 3 kGy,
without unduly aecting quality [40]. Thereby, strawberries can be harvested when fully
ripened and can be transported and displayed for longer periods while maintaining
desirable sensory qualities longer than nonirradiated strawberries.
From intact vegetable crops, apart from tuber, bulb, and root crops, tomatoes and
asparagus show potential for radiation treatment. The development of fungal decay in
tomatoes caused by Alternaria, Botrytis, or Rhizopus spp. can be controlled using doses of
approx. 3 kGy. However, softening and the loss of characteristic avor may occur. Doses
of 0.1 kGy and above result in a delay of ripening of tomatoes [43].
Irradiation (12 kGy) of fresh asparagus in combination with wrapping with
polyvinyl chloride (PVC) lm can double the shelf life under refrigeration with no eect
on color and avor [44].
4.6. Irradiation of Fresh Meat and Poultry
Increase of shelf life under refrigeration and control of pathogenic nonsporeforming
bacteria in fresh meat and poultry can be achieved by a 13 kGy dose. Doses for
irradiation are selected under the consideration of threshold dose levels for sensory
changes (o-odor), which depends on the type of animal meat (Table 7) [45]. O-odor
is due to the generation of volatile compounds from lipids and nitrogenous compounds
formed by the reaction of these constituents with the reactive species produced by the
radiolysis of water.
The considerable extension of the shelf life by doses as low as 1 kGy under aerobic
conditions is due to the radiation sensitivity of Pseudomonas spp. [46] and other Gram-
negative bacteria mainly associated with spoilage of fresh meat and poultry. Also, a
signicant reduction in the number of pathogens including Salmonella, Campylobacter,
Yersinia, Staphylococcus, Escherichia coli, and Listeria can be achieved in fresh or frozen
meat and poultry by radiation pasteurization [47,48]. The coliforms, including E. coli
O157:H7, are quite sensitive to ionizing radiation; thus a standard irradiation pasteuriza-
tion process with 1.52.5 kGy causes its 56 logs reduction in ground beef, and it would
reduce also Salmonella and Listeria monocytogenes by 24 logs [49]. In other recent studies
in Hungary, in comparison of gamma irradiation and high hydrostatic pressure-induced
eects on minced beef, radiation pasteurization proved to be superior in maintaining
quality [50]. Ground meat poses particular food safety concerns because the grinding
process can spread pathogens present on the meats surface throughout the product.
Recent results in the United States [51] showed that irradiation of pork trim with a
processing dose of min. 1.25 kGy and max. 1.9 kGy prior to production of dry fermented
sausage such as pepperoni can yield a sausage product with quality indicators closely
resembling those of the traditional dry sausage while still providing the 5-log reduction of E.
coli O157:H7 as mandated by the U.S. Department of Agriculture (USDA). A heat
treatment of the pepperoni sticks performed on the nished product to an internal temper-
ature of 60jC as decontamination alternative signicantly altered the texture and color.
Because freezing confers greater radiation resistance of microorganisms, higher
doses are needed under freezing [52] (see also Table 4) but the sensory results can be better.
One of the major concerns in irradiating meats is its eect of meat quality. Minced
beef is susceptible to lipid oxidation. However, our own studies in cooperation with the
University College Cork, Ireland [53], demonstrated that increased endogenous alpha-
tocopherol concentration by dietary vitamin E supplementation prior to slaughter of the
animals, and combination of this feeding supplementation with a rosemary extract as
natural antioxidant additive to the ground beef, resulted in a color-stabilizing and lipid-
protecting eect. Studies by Giroux et al. [54] also showed that incorporation of ascorbic
acid into the beef patties before irradiation (0.54 kGy) stabilize the color during
refrigerated storage, and its use in combination with irradiation increased the shelf life
Table 7 Threshold Doses for
Some Foods of Animal Origin for
an Organoleptically Detectable
O-Flavor
Food
Threshold Dose
a
(kGy)
Turkey 1.5
Pork 1.75
Beef 2.5
Chicken 2.5
Lobster 2.5
Shrimp 2.5
Rabbit 3.5
Frog 4.0
Trout 4.5
Halibut 5.0
Lamb 6.25
Horse 6.5
a
Irradiated at 510jC.
of ground meat without detrimental eects on taste and odor. Dark rm dry (DFD) pork,
highly susceptible to microbial spoilage, as a result of a higher pH than normal, was
resistant to oxidative changes; thus the microbial safety and the shelf life of DFD meat can
be signicantly improved by irradiation, thereby improving the utilization of raw DFD
pork [55].
Pink color formation in irradiated broiler breast llets after cooking, and the char-
acteristic irradiation odor, can be signicantly reduced through shelf display of raw llets
under aerobic conditions [56].
Radiation decontamination of meat was rst commercially implemented in Brittany,
France, when e-beam irradiation treatment was established for frozen slabs of mechan-
ically separated chicken meat [57,58].
Serious outbreaks due to contamination with and survival of enterohemorrhagic E.
coli in improperly cooked hamburger patties in the west coast of the United States in 1993
prompted a petition to the Food and Drug Administration (FDA) for approval of meat
irradiation. This approval was granted in 1997 in view of new outbreaks caused by this
pathogen and the subsequent recall of some 10,000 tons of ground beef because of
contamination with E. coli O157:H7 [59]. The nal rule authorizing irradiation of
refrigerated or frozen raw meat products permits the use of a dose of 4.5 kGy for
refrigerated meats and a dose of 7 kGy for frozen products [60].
4.7. Irradiation of Fish and Shellfish Products
Fish and many other shery products are perishable commodities with short shelf lives
even under refrigeration. Fish and shellsh can be contaminated by pathogenic micro-
organisms, either because of polluted water or handling after catch [61]. Irradiation could
eectively extend the storage life and reduce the levels of pathogenic organisms. The role
of radiation processing in the improvement of the hygienic quality of shery products has
been reviewed, e.g., by Venugopal et al. [62].
In a recent literature, Kamat and Thomas [63] reported that radiosensitivity of four
food-borne pathogens, L. monocytogenes, Yersinia enterocolitica, Salmonella typhimurium,
and Bacillus cereus was not inuenced by the fat content of Indian sh varieties and
application of 3 kGy dose at refrigeration temperature would eectively inactivate approx.
10
5
CFU/g of all the organisms tested, except spores of B. cereus. Savvaidis et al. [64]
reported recently from Greece that a shelf life of 28 days at 4jC was recorded for salted,
vacuum-packaged freshwater trout irradiated at 2 kGy, compared with a shelf life of 7
days for the unirradiated sample based on sensory odor scores. Under the same
conditions, the growth of L. monocytogenes inoculated into the samples was suppressed
by 2 log cycles after 2 kGy irradiation and storage for up to 18 days at 4jC.
The increased incidence of food-borne diseases from shellsh contaminated with
Vibrio species have brought forward renewed interest in irradiation of shellsh and other
seafood. Results are very promising for clams and oysters without killing the molluscs [65].
The radiation decimal reduction dose (D
10
) determined for Vibrio cholerae O1 biotype El
Tor inoculated into various molluscs was 0.14 kGy [66]. Similar radiation sensitivity of
this organism was found in inoculated sh llets and shrimp tails [67]. The radiation dose
to eliminate as high as 10
7
CFU/g Vibrio spp. in oysters was 1.2 kGy [68]. The radiation
D
10
value for V. cholerae O1 biotype El Tor in marine snails was 0.11 kGy [69].
Petitions by the National Fisheries Institute for approval of irradiation treatment to
control food-borne pathogens in raw or processed crustaceans are pending at the
regulatory authorities in the United States [70].
In France, most, if not all, frog legs marketed are being treated by irradiation to
ensure their hygienic quality [71].
4.8. Irradiation of Minimally Processed or Ready-To-Eat Foods
Minimally processed is an equivocal term that is applied to such dierent types of
products as precut, prepackaged fresh produce, and mildly cooked or pasteurized foods
(meals or meal components) that can be stored under refrigeration for more than 1 week.
Some conventional products such as cured meats can be considered as minimally
processed but more frequently a new generation of partially processed, refrigerated foods
are described with this term.
There is an increasing consumer trend and interest by the catering industry toward
less extensively processed, convenient, or ready-to-eat foods. In response to the demands,
minimally processed foods are gaining importance, and consumers perceive these foods to
be superior because they are chilled rather than canned, dried, or frozen [72].
Many fresh-cut produce takes the advantage of the internal development of a
modied atmosphere packaging (MAP), which improves the retention of quality under
delicate interaction between respiratory increase of CO
2
, gas transmission properties of
packaging materials, and storage temperature.
Various mildly cooked chilled product are also marketed under MAP, packaged with
elevated concentrations of CO
2
over the product. CO
2
suppresses the growth of aerobic
spoilage bacteria. Special versions of cook-chill foods are the sous-vides. Sous-vide is a
process where the food is cooked under controlled conditions of temperature and time
under 100jC inside heat stable, vacuumed plastic pouches [73].
The safety of all these foods largely depends on the temperature of refrigerated
storage and eventually on other hurdles to microbial growth (reduced pH, reduced water
activity, or antimicrobials). With the extended shelf life, there are opportunities for growth
of surviving psychrotrophic microorganisms, and even mesophilic species in case of
abusive temperature.
In products prepared without pasteurization, nonsporeforming as well as sporeform-
ing pathogens should be considered as potential hazard. With mildly cooked minimally
processed food, the pathogens of greatest concern are the psychrotrophic nonproteolytic
types of Clostridium botulinum and certain strains of B. cereus [74].
Considering the generally quality-friendly character of treatment with ionizing
radiation, and by adopting a hazard analysis and critical control point (HACCP)-
based approach to risk management, irradiation processing oers a physical critical
control point for improving microbiological safety of minimally processed foods [75,76].
(A critical control point is a point, step, or procedure at which control can be applied and
a food safety hazard can be prevented or reduced to acceptable level.)
Regarding irradiation of minimally processed fresh produce, irradiation treatment at 1
kGy reduced the viable cell count of L. monocytogenes inoculated onto precut packaged
vegetables such as sliced bell pepper, carrot cubes, shredded white cabbage, and sliced radish
[77]. The irradiation also drastically reduced the viable load of spoilage bacteria thereby
improving the microbiological shelf life and extending the sensorial keeping quality of the
precut vegetables. Loss of vitamin C content as an eect of irradiation did not exceed that in
untreated samples throughout their useful life. Similarly, the benecial eects of irradiation
at 1.0 kGy of diced celery were reported by Prakash et al. [78].
Howard et al. [79] reported promising results on the eects of gamma radiation
processing (1 kGy) for extending the shelf life of refrigerated pico de gallo, a Mexican-
style cold salad prepared by chopping and mixing fresh tomatoes, onions, and jalepeno
peppers. Microbiological shelf life and microbiological safety of diced tomatoes and
cantaloupes could be improved at 0.51.0 kGy without signicant loss of consumer quality
[80,81]. Similarly, low doses of 0.35 and 0.55 kGy can improve the safety and micro-
biological shelf life of cut romaine lettuce packaged under modied atmosphere and
shredded iceberg lettuce, respectively [82,83].
Ionizing radiation eectively inactivates nonsporeforming pathogenic bacteria also
from cured or cooked meats [84]. Pathogen reduction and shelf life extension in cooked
pork chops and cured hams inoculated with L. monocytogenes and S. typhimurium were
studied by Fu et al. [85]. Low-dose irradiation (0.750.9 kGy) reduced L. monocytogenes
by more than 2 logs and S. typhimurium by 1 to 3 logs. Alur et al. [86] described
eradication of Salmonella and Staphylococcus from several processed pork products in
India by gamma radiation doses of 2.54 kGy. When Sommers and Thayer [87] surface-
inoculated several brands or types of commercially available frankfurters with a cock-
tail of four L. monocytogenes strains and vacuum packaged, the gamma radiation D
values ranged from 0.49 to 0.71 kGy depending on the individual product formulation.
The eect of irradiation (2 and 3 kGy) and storage at 23jC on the sensory quality
of cook-chill ready meals consisting of roast beef and gravy, and cauliower together with
roast and mashed potatoes were assessed by McAteer et al. [88]. The authors noted that
growth of Pseudomonas spp. caused obvious spoilage of the nonirradiated meals after 15
days of storage, whereas irradiation reduced the number of microorganisms in the meal to
less than 100 CFU/g initially, and signicant microbial growth did not occur during the
entire storage. However, using sensory proling techniques, a trained panel found that the
organoleptic eects of irradiation and chilled storage were most apparent in the cauli-
ower and mashed potato components, and mostly occurred in the color, appearance, and
textural attributes. In another study, the same research group performed a consumer trial
with 107 consumers to assess the acceptability of an irradiated (2 kGy) chilled meal
consisting of beef and gravy, Yorkshire pudding, carrot, broccoli, and roast potato. The
testing after 4 days after radiation treatment indicated that untrained consumers found
the irradiated meal moderately to very acceptable, and not signicantly dierent from the
nonirradiated meal [89]. Only for the Yorkshire pudding was there a signicant dierence
between the nonirradiated and irradiated samples.
In a later series of experiments on other types of ready-to-eat meals (roast pork and
gravy and mixed vegetables), 2 kGy was selected as the most appropriate irradiation dose
[90]. Microbial numbers in control meals reached unacceptable levels by 6- and 4-day at
3jC and 10jC, respectively, while samples irradiated at 2 kGy remained acceptable
throughout the 14-day storage at 3jC, but irradiated samples stored at 10jC had
unacceptably high numbers by day 6. The 2 kGy radiation dose reduced thiamin content
in the pork component of the ready-to-eat meal by 22%. After storage at 3jC for 14 days,
a further 26% thiamin loss was measured, and a further 14% decrease occurred when the
meals were reheated as per the manufacturers instruction at 160jC for 25 min. Irradiation
caused 51% loss in total vitamin C content of potatoes in the ready meals. The vitamin C
content of potatoes greatly decreased in both nonirradiated and irradiated potatoes during
storage. Reheating had a highly detrimental eect on the levels of vitamin C.
In a recent study in the United States, irradiation of a prepared meal consisting of
Salisbury steak, gravy, and mashed potatoes at 5.7 kGy eectively eliminated the back-
ground microbial population and high concentrations of L. monocytogenes contamination
without causing adverse eects on quality [91].
Sous-vide cooking is thought to be quality friendlier than regular cooking due to the
mild heat treatment and vacuum packaging. The combined eect of irradiation and sous-
vide cooking of chicken breast meat was investigated with respect to survival and growth of
L. monocycotenes, shelf life, thiamin content, and sensory quality by Shamsuzzaman et al.
[92]. Combining electron irradiation of 2.9 kGy and cooking in vacuum packaging to an
internal temperature of 65.6jC, reduction of more than 5.5 logs of CFUs of L. mono-
cytogenes was achieved and the pathogen remained undetectable in the irradiated product
during an 8-week storage at 2jC. Regarding the general microbiological quality, the product
that received the combined treatment had at least 8 weeks shelf life under refrigeration. The
electron beam treatment had little eect on odor and avor, and the thiamin content was
reduced by only 5%. In a second experiment [93], the same product inoculated with L.
monocytogenes to approx. 10
6
CFU/g was cooked to 71jC. This sous-vide cooking alone
reduced Listeria counts by only 1.5 log cycles; the survivors multiplied quickly during the
8jC storage and nonirradiated samples spoiled within 2 weeks. The combination of 3.1 kGy
and sous-vide cooking reduced Listeria counts to undetectable levels without adversely
aecting the sensory quality and prevented microbial spoilage for at least 8 weeks. The loss
of thiamin content due to combined treatment varied from 23% to 46%.
In studies of Farkas et al. [94], the survival and growth of spores of a psychrotrophic
B. cereus strain inoculated in a meal of smoked-cured pork in boiled beans sauce were
investigated as aected by combination of 5 kGy and sous-vide cooking and storage time
at 10jC. The microbiological analyses demonstrated that this medium dose irradiation
prior to sous-vide cooking sensitized surviving spores to the subsequent heat treatment
and provided microbiological stability for at least 2 months.
4.9. Radiation Decontamination of Dry Food Ingredients
The microbiological action of ionizing radiation is well proven to decrease the viable cell
counts in dry food ingredients, thus improving the microbiological safety of such products
and enhancing the storage stabilities of foods prepared with them. Spices, dry vegetable
seasonings, herbs, protein preparations, and commercial enzyme preparations used in the
food industry can be suciently decontaminated with doses of 310 kGy without altering
their avor, texture, or other important technological and sensory properties. It is also of
practical signicance that the surviving microora of radiation-pasteurized ingredients,
consisting mainly of bacterial spores, becomes more sensitive by the radiation treatment to
subsequent food processing treatments than the microora of untreated ingredients
[95,96]. Heat processing techniques have a much more limited feasibility of these
commodities because of the heat sensitivity of many of these ingredients. The irradiation
process is a viable alternative to the formerly used fumigation with ethylene oxide, which
was prohibited by a European Union (EU) directive in 1991 and has been banned in a
number of other countries, too, for health, environmental, or occupational safety reasons,
due to its carcinogenicity [97].
A detailed monograph on irradiation of dry food ingredients has been published in
1988 [98], and an updated shorter summary appeared recently [99]. A Code of Good
Irradiation Practice for the Control of Pathogens and Other Microora in Spices, Herbs,
and Other Vegetable Seasonings has been issued by the International Consultative Group
on Food Irradiation [100].
Presently, irradiation of spices is the most widely utilized application of food
irradiation that is practiced in more than 20 countries, including Argentina, Belgium,
France, Hungary, Mexico, The Netherlands, Norway, South Africa, and the United
States, and global production of irradiated spices has increased from about 5000 tons in
1990 to over 60,000 tons in 1997. In the United States alone, over 30,000 tons of spices,
herbs, and dry vegetable seasonings were irradiated in 1997, as compared to only 4500
tons in 1993 [101]. In 1999, about 95 million pounds of these products were irradiated
accounting for about 10% of their total consumption [102].
In addition to reducing microbial contamination, irradiation is an eective method
for increasing of extraction yield of medicinal herbs [103].
4.10. Combination Processes in Food Irradiation
When irradiation is used with other preservative or antimicrobial factors, the global
eciency is reinforced through additive or synergistic action. The combination of irradi-
ation with mild heat treatment has a number of advantageous eects [104]. The possibility of
using heat in combination with irradiation was rst suggested in the 1950s when synergistic
eects were observed with a variety of biological systems including bacteria. More recently,
Thayer et al. [105] investigated the eects of heat and ionizing radiation on S. typhimuriumin
mechanically deboned chicken meat and reported that irradiation to a dose of 0.9 kGy
caused heat-sensitization of S. typhimurium.
The synergy between irradiation and heat, coupled with the persistence of the
radiation-induced heat sensitization, could be used to advantage in foods that are cooked
before consumption, and cook-chill ready meals that are reheated prior to consumption
[106] (see also Sec. 4.8).
The synergistic eect of irradiation plus heat on vegetative organisms may be due to
the inability of cells to repair radiation damage because heating might inactivate repair
enzymes. In bacterial spores, the synergism [107] may be related to the partial rehydration
of the spore core due to the radiation-induced degradation of the cortex peptidoglycan
that is providing otherwise an osmoregulative eect maintaining the dehydrated state of
the core [108]. A recent paper [109] demonstrated a method to quantify the radiation-
induced sensitivity of bacterial spores to heat in conduction heating foods and illustrated
the associated savings in the heating cycle of the ultimate thermal process.
Mild heat treatment such as a hot water dip in combination with low-dose
irradiation found to be ecient to decrease rot and without adverse eect on nonmicrobial
qualities of certain fruits such as mangoes [110,111] and clementines [112].
In the eld of muscle foods, the use of marination before irradiation reduced the
dose necessary to eliminate Salmonella in poultry [113]. Some antimicrobial additives,
especially the natural ones (e.g., bacteriocins) [94] and GRAS (generally recognized as
safe) preservatives [114] can be usefully combined with irradiation to reduce dose
requirements. Some antioxidants have also been used to prevent the undesirable oxidative
eects in irradiated foods.
4.11. Radiation Sterilization of Food (Radappertization)
The purpose of this process is the production of foodstus that are shelf stable at ambient
temperatures and that have better quality characteristics than the corresponding heat-
sterilized products. Radappertization dose of low-acid foods must ensure elimination of
the spores of the most resistant bacterial pathogen, C. botulinum. The dose selected for the
purpose is around 50 kGy, 12 times of the D
10
value. As the product is intended to be
shelf-stable at ambient temperature, while autolytic enzymes have high radiation resist-
ance, the radiation treatment is supplemented with a mild heat treatment to inactivate the
enzymes. This high-dose treatment must be delivered to a vacuum-packaged and deeply
frozen (30jC, or less) product to avoid avor changes [115]. The whole process thus
involves the following steps:
1. Heating to an internal temperature of 6575jC.
2. Packaging under vacuum in a sealed container impermeable to moisture, air,
light, and microorganisms.
3. Cooling/freezing to irradiation temperature.
4. Irradiation.
The technology has been developed mainly for meats, poultry, and certain seafoods
in the United States, and radappertized foods were successfully used in space missions
[116]. Similar radiation-sterilized products were manufactured by the Atomic Energy
Corporation of South Africa for hikers [117].
Radiation sterilization of deep frozen meals prepared for hospital patients whose
immune systems have been suppressed is approved in several countries such as the United
Kingdom, The Netherlands, and the Federal Republic of Germany.
5. WHOLESOMENESS OF IRRADIATED FOODS
Wholesomeness (toxicological innocuity, nutritional adequacy, and microbiological
safety) of irradiated food has been carefully evaluated by an unprecedented width of
research and testing over more than 50 years. All scientically acceptable evidence
resulted from these studies supports the safety of irradiated foods for consumption
[14,118121].
At low and medium doses, it is well established that the nutritional value of proteins,
carbohydrates, and fats as macronutrients are not signicantly impaired by irradiation,
and neither the mineral bioavailability is impacted. Like all other energy depositing
process, the application of ionizing radiation treatment can reduce the levels of certain
sensitive vitamins. Nutrient loss can be minimized by irradiating food in a cold or frozen
state and under reduced levels of oxygen. Thiamin and ascorbic acid are the most
radiation sensitive, water-soluble vitamins, whereas the most sensitive, fat-soluble vitamin
is vitamin E. In chilled pork cuts at the 3 kGy maximum at 010jC, one may expect about
3540% loss of thiamin; in frozen, uncooked pork meat irradiated at a 7 kGy maximum at
20jC approx., 35 % loss of it can be expected [122].
The Joint Food and Agriculture Organization (FAO)/International Atomic Energy
Agency (IAEA)/World Health Organization (WHO) Expert Committee on Food Irradi-
ation (JECFI) has evaluated the very extensive literature on wholesomeness of irradiated
food and concluded already in 1980 that ...the irradiation of any food commodity up to
an overall average dose of 10 kGy presents no toxicological hazard, hence, toxicological
testing of foods so treated is no longer required, and . . .irradiation of foods up to an
overall average dose of 10 kGy introduces no special nutritional or microbiological
problems [119]. Independent evaluations by experts, e.g., in Denmark, France, Japan,
The Netherlands, the United Kingdom, and the United States found neither toxic eects
as a result of consuming irradiated food. The FAO/WHO Food Standards Program,
Codex Alimentarius, accepted the JECFIs recommendations and established a Codex
General Standard for Irradiated Food and a Recommended International Code of
Practice for the Operation of Radiation Facilities used for the Treatment of Foods [6].
There is no evidence or reason to expect that irradiation produces more virulent pathogens
among those that survive irradiation treatment [123,124].
After publishing an up-to-date review on safety and nutritional adequacy of
irradiated food [120], the FAO/IAEA and the WHO jointly conveyed a Study Group
on High Dose Irradiation in 1997, which reviewed all relevant data related to the
toxicological, microbiological, nutritional, radiation chemical, and physical aspects of
food exposed to doses greater than 10 kGy. The Study Group came to the conclusion that
foods treated also with doses of radiation sterilization can be considered safe and
nutritionally adequate when produced under established Good Manufacturing Practices,
and recommended approval of food irradiation without any dose maximum limit [121].
The recommendation has been submitted to the Codex Alimentarius Commission for
possible amendment of the 1984 Codex General Standard on Irradiated Foods.
6. LEGISLATION OF FOOD IRRADIATION
The WHO closely collaborates with its Member States and the other international
organizations, particularly through the International Consultative Group on Food
Irradiation (ICGFI) established in 1984 under the aegis of FAO, IAEA, and WHO.
Through the eorts of the ICGFI, which had a membership of 46 governments in 1998,
harmonized regulations on food irradiation are being promulgated in developing countries
in Asia, the Pacic, Africa, Latin America, and the Middle East [125]. The ICGFI issues
numerous publications relating to food irradiation, including codes of good irradiation
practice for various classes of foods [126] and compilations of technical data for author-
ization and control of food irradiation.
All these international documents and activities of the specialized agencies of the
UN facilitated legislation of food irradiation in many countries. According to the
database developed by the ICGFIs Secretariat at the Food and Environmental Pro-
tection Section of the Joint FAO/IAEA Division in Vienna, currently some 50 countries
granted national clearances of irradiation of at least one or more food items of food
classes. The itemized ICGFI database on these clearances can be visited on the website
http://www.iaea.org/cgi-bin/rifa-ste.1. Legislatory authorities require that irradiated food
products be labeled. In general, the international food irradiation symbol, the so-called
Radura logo:
is required with a statement that the product has been intentionally subjected to
radiation. The severity of labeling requirements for multi-ingredient products to identify
irradiated components on the list of ingredients is not the same with each authority.
After 10 years of debate, the European Parliament and the Council of the European
Union issued on February 22, 1999, a framework Directive 1999/2/EC on approxima-
tion of the laws of the Member States concerning foods and food ingredients treated with
ionizing radiation [127], and a Directive 1999/3/EC on the establishment of a Community
List of foods and food ingredients treated with ionizing radiation [128]. The present
category of foodstus authorized by this Directive for irradiation treatment is dried
aromatic herbs, spices, and vegetable seasonings, and the permitted maximum overall
average absorbed dose is 10 kGy. The Directive enforces strict labeling. Unfortunately, all
requisite labeling of irradiated foods appears much more in the form of a warning than an
item for neutral information.
Working on the subject between 1986 and 1998, the EU Scientic Committee of
Food (SCF), an independent expert body advising the European Commission on health
matters, concluded that the food irradiation process posed no problem for health over a
wide ranged of uses, if used under prescribed conditions and endorsed for authorization of
17 irradiated foods/food classes [129]. The Commission proposal in December 1998 for an
EU directive contained eight food categories and three products.
By the published Directive 1999/2/EC, the European commission was charged to
develop a nal positive list of permitted items until the end of 2000, but the contents of
this list are not yet published. There was even a consultation on this problem on the
Internet and industry and consumer organizations responded [130]. As long as the
positive list is not adopted, Member States can maintain the existing regulations except
for spices [131].
Regarding packaging materials for irradiated foods, most commonly used food
packaging material are suitable for the purpose. However, irradiation of prepackaged
food requires approval of its packaging material [132].
7. FOOD IRRADIATION PROCESS CONTROL AND DETECTION OF
IRRADIATED FOODS
Proper control of food irradiation applications should fulll the requirements for both
food technologies and radiation technologies. Application of well-established methods for
measurement of absorbed radiation dose and the dose distribution helps to provide
assurance that the radiation treatment is both eective and legally correct [133]. Computer
tomography (CT) can provide detailed, high-resolution, and accurate dose maps for any
arbitrary product and package congurations [134]. Such dose maps are an essential part
of process validation.
Signicant progress has been made in the eld of analytical detection of irradiated
food to improve consumers condence and to assist international trade of irradiated food
[135,136]. Due to national and international programs and activities of the European
Committee for Standardization (CEN), ve validated and standardized detection methods
are now available. The CEN is also considering the adoption of further ve detection
methods: three will be screening methods (positive results from a screening method must
be conrmed using a standardized method) [136].
One of the standardized methods, electron spin resonance (ESR) technique, permits
identication of food that contains a hard, dry matrix, e.g., bone. When food containing
bone is irradiated, free radicals are produced and trapped in the crystal lattice of the bone,
which can be detected by ESR spectroscopy [137]. Thermoluminescence of contaminating
minerals for detection of radiation treatment of, e.g., spices and dried fruits can be
successfully applied [138, 139]. Another standardized method that has been developed for
identication of irradiated fat-containing foods is the mass-spectrometric detection of
radiation-induced 2-alkylcyclobutanones after gas-chromatographic separation [140]. The
DNA comet assay (analysis of DNA fragmentation by irradiation) can be applied as a
fast and simple screening method [141]. For simple screening of irradiation decontami-
nation of dry ingredients of high starch contents, viscosity measurements of their heat-
gelied suspensions is suitable because of their reduced viscosity due to the radiation-
induced starch damage [142144].
8. ECONOMIC FEASIBILITY OF FOOD IRRADIATION
The costs of irradiation are inuenced by a large number of factors depending on the actual
use and local conditions. To optimize processing costs, one must fully understand the
processing scenario and then design an industrial facility that best matches it [145]. The
many dierent potential applications of food irradiation create many dierent requirements
in irradiator design [146]. The throughput requirement can range from a few to hundreds
of tons per hour. With such a variety of process specications discussed in the previous
chapters, the cost of irradiating food also substantially varies from one application to
another. As any other processing technologies, due to varying conditions, cost of the same
type of treatment may dier from place to place, and a cost estimate in one country is not
necessarily representative of other countries.
The capital costs to build a commercial food irradiation plant is about a fewmillions of
U.S. dollars but within the range of plant costs for other physical methods of food pre-
servation. Total annual operating costs are close to $1 million. The total processing cost is
the sumof the total operating costs plus the cost of money, and the depreciation of capital
(amortization) [146]. The unit cost of irradiation equals the total annual processing costs
divided by the annual throughput. This unit processing cost in all irradiators rapidly
decreases with the initial increase of throughput because the xed costs are spread over a
larger number of units [147]. The economic throughput is a function of many factors and
these economics on scale are very pronounced at smaller sizes [148]. The eect of increasing
dose on unit processing costs is linear because unit processing costs inversely relates to
annual throughput.
The ICGFI [149] estimates that irradiation cost range from $10 to $15 per tonne for
a low-dose application (e.g., inhibition of sprouting of potatoes or onions), and $100 to
$250 per tonne for a high-dose application (e.g., to ensure hygienic quality of spices).
These unit costs are considered to be competitive with alternative treatments.
In addition to economic feasibility, radiation processing is less energy consumptive
than other decontamination techniquesan increasingly encouraging feature of radiation
technology [150].
9. RECENT DEVELOPMENT OF COMMERCIAL IMPLEMENTATION OF
FOOD IRRADIATION
Acceptance of irradiated food was greatly inuenced by the perception of food irradiation
as a nuclear technology. As Professor J.F. Diehl, one of the world authorities in food
irradiation, rightly points out [151]: Much more than other modern methods of food
processing, food irradiation has to overcome barriers created by prejudice, misleading
information, restrictive legal and regulatory measures, and a resulting reluctance of food
manufacturers and food trade to make use of the new technology. A signicant barrier to
adoption of the irradiation technology was the wait and see attitude of the food
industry and trade because they either perceived signicant consumer resistance or because
they had concerns about being seen as the leader in a technology perceived as controversial
[125]. Still much needs to be carried out for the wider commercial application of the
technology and public understanding and acceptance of irradiated food. However, in spite
of certain anti-irradiation groups that have been eecting slow take-o of food irradiation
at work with the news media, the notion of overwhelming consumer resistance to the
technology is a myth and a changing attitude can be noted on market research studies.
Numerous consumer acceptance studies and market tests in several countries during the
past decades indicate that majority of the consumers are willing to purchase irradiated
food once they understand the safety and benet of the process [152155]. A group of
rejectors is that segment that generally rejects any new product and no amount of in-
formation would convince this group [156].
Besides the pioneering implementations of specic low-dose applications as well as
the widely utilized irradiation of spices now, mentioned in Secs. 4.1, 4.2, and 4.9, small-
scale commercial application of irradiation to ensure hygienic quality of food, especially
those of animal origin, has been carried out in Chile, China, Indonesia, and Thailand in
the past two decades. In the recent years, new commercial irradiators including some that
are dedicated to food irradiation have been commissioned in Brazil (which plans to add up
to 10 facilities in the coming years), China, India, Republic of Korea, Mexico, and
Thailand [157].
Very important recent progress is noted in the United States. Following the approval
in December 1999 of irradiation of refrigerated or frozen raw meat and meat products to
eliminate or signicantly reduce E. coli O147:H7 and other hazardous bacteria, in May
2000, commercial production and marketing of irradiated frozen beef patties started,
electron-beam treated by Sure-Beam Corp., Sioux City, Iowa. This irradiation plant can
process yearly more than 100 thousand tons of beef [158]. The other irradiation company,
Food Technology Service, Inc., Mulberry, Florida, which has been irradiating poultry
since 1996 with its MDS Nordion-designed cobalt-60 plant, also began treating fresh
ground beef and frozen beef patties. The Ion Beam Applications (IBA) company was
expected to complete in mid-2001 a 135 kW electron accelerator to be used in x-ray mode
for food. Because several other irradiation plants are under construction in various states
in the United States [159], a nationwide distribution of these irradiated products becomes
possible. Due to low conversion rate of production of x-rays, the x-ray technology is
probably not as economical in food irradiation as gamma rays or electron beam
technology. Nevertheless, an x-ray plant has been recently constructed in Hawaii to
disinfest tropical fruit [160]. An important step toward wider future applications is a
petition in 1999 to the FDA, for approval of irradiation of many types of ready-to-eat
food by the Coalition of Food Irradiation, which involves approx. 25 dierent associa-
tions of food producers.
Due to legislative stumbling blocks (described in Sec. 6), after early pioneering eorts
in several countries, e.g., Netherlands, France, and Belgium, where considerable amounts
of frozen seafood, frog legs, and dry food ingredients have irradiated already been in the
1980s, progress in Europe is now lagging behind the developments in the United States.
However, increasing activities on food irradiation in the United States, which is one of the
largest markets in the world, and also similar activities in some countries of Asia and Latin
America, will likely inuence other countries and regions to implement the use of
irradiation for commercial purposes.
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27
New Applications of Ion Beams to Material,
Space, and Biological Science and Engineering
Mitsuhiro Fukuda, Hisayoshi Itoh, Takeshi Ohshima, Masahiro Saidoh,
and Atsushi Tanaka
Japan Atomic Energy Research Institute, Takasaki, Gunma, Japan
1. INTRODUCTION
Ion accelerators rst appeared around 1930 and began growing rapidly in the 1930s. At the
beginning of the growth period, the ion accelerators were originally designed as exper-
imental equipment required for nuclear physics and for radioisotope production. A variety
of ion accelerators has so far been developed in succession to meet the demands from
nuclear research. The beginning of the ion beam applications, except for nuclear research,
was the medical application to the treatment of tumors with charged particles started in the
1950s. For industrial applications of ion accelerators, ion implantation began in the middle
of the 1960s. The use of ion beams for material analysis became widespread in the 1970s. The
full-scale applications of MeV ion beams to materials, bio-, medical, and life sciences have
rapidly broadened in the 1990s.
So far, there is no ion accelerator facility adapted for biological or botanical research,
ion beamprocessing research, etc., because of the lack of the strong incentive to the research
using accelerator ion beams. The ion beam irradiation research facility, Takasaki Ion
Accelerators for Advanced Radiation Applications (TIARA), may be the rst facility to
promote the research on a large scale. The facility was completed in 1993 at the Takasaki
establishment of Japan Atomic Energy Research Institute (JAERI), and the extensive
applications of ion beams have been conducted mainly for research and development in
materials science and biotechnology under full-scale operation of the azimuthally varying
eld (AVF) cyclotron and three electrostatic accelerators [1]. In this chapter new applica-
tions of accelerated ion beams to materials, space, and biological science and engineering,
carried out mainly at TIARA, have been reviewed. Various ion beam technologies pioneer-
ing ion beam applications have also been described.
2. CHARACTERISTICS OF ION BEAMS INTERACTING WITH MATTER
When energetic ions penetrate into matter, energy deposition from incident particles to the
irradiated mediumoccurs through a variety of interactions between the incident particle and
the constituent atoms or molecules of the irradiated medium. In general, energetic, heavy
charged particles transfer their energy to the irradiated materials with high-density ioniza-
tion and excitation along their nearly straight particle tracks (even for uniform irradiation)
showing a maximum linear energy transfer (LET) in the curve of dose distribution against
penetration depth until the particles are brought to rest. This characteristic results in micro-
scopically nonuniformdose delivery having a specic dose distribution against depth, which
are in contrast to relatively uniformdose delivery and monotonous dose distribution against
depth in low-LET radiation irradiation such as gamma-ray and electron beam irradiation.
Another important characteristic is that ion beams can produce a variety of the
secondary particles/photons such as secondary ions/atoms, electrons, positrons, X-rays,
gamma rays, and so on, which enable us to use ion beams as analytical probes. Ion beam
analyses are characterized by the respectively detected secondary species, such as secondary
ion mass spectrometry (SIMS), sputtered neutral mass spectrometry (SNMS), electron
spectroscopy, particle-induced X-ray emission (PIXE), nuclear reaction analyses (NRA),
positron emission tomography (PET), and so on.
In addition to the above-mentioned features, the ion beamirradiation has functions of
implantation of dierent atoms in the irradiated medium and of the nuclear transmutation
of the irradiated medium atoms. So far, the underlying physics and the subsequent
relaxation processes in the interaction between ion beams and matter have been extensively
studied not only for purely scientic interests but also for practical purposes, such that a
series of international conferences on these topics have been held on a worldwide scale [2].
The relationship between the properties of the ion beams interacting with matter and
the parameters of ion beam applications is shown in Fig. 1. Recent progress of ion beam
handling technologies such as microbeam and single-ion hit techniques enable us to apply
ion beams for advanced research and development in materials science and in biotechnol-
ogy, such as the analysis of the single-event eect in the semiconductor device for space, the
radiation processing of microscopic region, cell surgery technique, simulation of radiation
risk for human space ight, and so on.
Figure 1 The relationship between properties of the ion beams interacting with matter and items of
ion beam applications.
3. ION BEAM TECHNOLOGIES PIONEERING THE ION BEAM
APPLICATIONS
3.1. Diversity of Ion Beam Irradiation Techniques
The most interesting parameters of the ion beams used for the nuclear research are mass
number, atomic number, energy, and intensity of the accelerated particles. Special irradi-
ation techniques are not always required for the nuclear research. In contrast, irradiation
properties for the ion beam applications to materials science and biotechnology have been
widely diversied to fulll the requirements of the research. The optimum irradiation
condition depends on howwe want to bring about physical, chemical, or biological eects in
a target substance, and how we investigate characteristics of the substance skillfully. The
extent to which ion-induced eects are controllable and the analyzing techniques can be
highly sophisticated by optimizing physical parameters of the ion beam, such as ion species,
energy, beam intensity, irradiation area, particle density uence, incident angle, and so on.
The fundamental parameters of the ion beam irradiation are shown in Fig. 2. The response
to the ion beamirradiation depends on the phase of the substance (gas, liquid, solid) and on
temperature, atmospheric pressure, and so on.
Controllability and exibility of the irradiation parameters are indispensable for the
ion beam applications. The widely diverse requirements for the irradiation conditions have
promoted the development of various ion beam technologies. Conversely, there are some
cases that new ion beam technologies trigger a breakthrough in the ion beam applications.
Nowadays, it is no exaggeration to say that the ion beam technologies are pioneering new
research elds. The ion beam technologies classied according to the irradiation conditions
are listed in Table 1. The present status of the representative ion beam technologies is
described in the following sections.
3.2. Production of the Ions
Ion Source
Avariety of ion species, fromlight to heavy ions, namely, fromprotons to uraniumions, are
utilized for the ion beam applications. Wide diversity of ion species, charge state, and beam
currents is required to meet the requirements for the research of the ion beam applications.
Various types of ion sources [3], using dierent ionization methods, such as eld ionization
and surface ionization, have been developed to provide optimum ion beams. An ion source
Figure 2 Typical parameters of the ion beam irradiation.
of radio frequency (rf) plasma type produces positively or negatively charged particles by
ionizing gaseous atoms and/or molecules in the plasma. The constituents of the plasma are
the ions, electrons, and neutral atoms and/or molecules. The plasma remains stable by
conning the ions and electrons with a magnetic eld. The maximum ionization eciency is
obtained at electron energy about as high as 3 to 4 times the ionization potential of the
constituent atoms and/or molecules. A gas or a vaporized metal is fed into the plasma
generated by a discharge using microwaves or energetic electrons. The ions inside the
plasma are extracted by an electric eld formed between an ion reservoir and a perforated
electrode on which a high voltage is applied. The beamintensity is fully dependent on the ion
and electron densities in the plasma, the plasma electron temperature, the extraction
voltage, and the geometry of the extraction system.
Higher charge states have a great advantage of increasing the particle energy, since the
energy gain of the ions in the accelerator is proportional to the charge state. An electron
cyclotron resonance (ECR) ion source [4], using the eld ionization method, is substantially
superior in the performance of heavy-ion production with higher charge state. A schematic
drawing of a typical ECR ion source is shown in Fig. 3. The electrons in the plasma are
heated by rf power. Energetic electrons and high-density plasmas are required to produce an
intense beam of highly charged ions. A higher magnetic eld enables one to achieve an
ecient electron connement [5]. The plasma density is related to the square of the rf
frequency. To produce very intense beams, development of a superconducting ECR ion
source working at a higher frequency
f
28 GHz is in progress [6]. Nowadays, the ECR ion
source is widely used for various kinds of accelerators.
Cluster Ion Beam
A cluster ion beam, which is composed of atomic particles such as C
n
+
and Au
n
+
, where n is
the number of atoms in the cluster [7], or molecular ions such as OH
and AlO
+
, has
attracted a great deal of interest in atomic physics [8,9] and in materials science [10]. The
cluster ion beam has distinctive properties of vicinity eects caused in substances, which is
Table 1 Ion Beam Irradiation Parameters and Their Related Ion Beam Technologies
Parameter Requirement Ion beam technology
Ion species Variety Ion source
Cluster ion source
Multiplex ions Dual/triple beam
Energy Wide range from keV to GeV Accelerator
Quick change Cocktail beam acceleration
Intensity Wide range from a single
ion to mA
Ion source
Accelerator
Single-ion hit technique
Irradiation area and
particle density
uence
Uniformity Beam defocusing and a scatterer
Beam scanning: raster scan,
beam wobbling, spiral scan
Beam spot and
targeting resolution
Minimization
Precision
Microbeam and nanobeam
Micro-PIXE analysis
Time structure Flexibility Pulsated beam
rather dierent from those of a single ion. By irradiation of the high-energy cluster ion
beam, a number of atoms are implanted simultaneously into a very small area, bringing
high implantation density and large energy transfer. It is anticipated that the cluster ion
applications will result in a breakthrough in the invention of new functional materials.
Cluster ion sources with dierent production techniques have been devised [10]. The
cluster ions are produced, for instance, by vaporizing the materials using a heated oven, a
laser ablation apparatus, or sputtering. Essential features of the cluster ion source are
increased intensity and stability of the beam, and control of the mass distribution of the
particles. Further development of cluster ion sources is in progress at several facilities [7,11].
3.3. Acceleration of Ions
Ion Accelerator
Ion beams are powerful tools for modication of specic material characteristics, inves-
tigation of material properties, and processing and creation of materials, bringing great
benet to industrial applications. Ion beams in the energy region of
f
keV to several MeV
have the advantage of enhancing the eectiveness of ion interaction with matter without
signicant damage. On the other hand, the ion beams of energy greater than several tens of
MeV cause great damage to the substances along their trajectory. With larger range and
higher LET in substances, the high-energy ion beams are typically utilized for investigating
the radiation tolerance of materials, for creating new materials, and for generating new
plant resources.
Figure 3 A schematic drawing of a typical ECR ion source. The ions and electrons are conned in
the plasma by the magnetic eld generated by the solenoid coils and the hexapole magnet.
Ion accelerators can cover a wide range of energy from
f
keV to
f
GeV, depending
entirely on the requirement of the application. A single accelerator can hardly provide
various ion beams in such a broad dynamic range of energy due to limitations of the
acceleration voltage, the magnetic eld, beam quality, and other reasons. Practically, the
required energy range may be covered by a combination of dierent accelerators like the
accelerator complex at the TIARA facility of JAERI, Takasaki, as shown in Fig. 4 [12].
In principle, a charged particle is accelerated by traversing an electric eld formed
between electrodes. Acceleration methods are classied into two types: potential acceler-
ation using static elds and sequential acceleration using alternating elds [13]. Electrostatic
accelerators such as the Van de Graa accelerator and a tandem accelerator, belonging to
the former type, provide ion beams with energy of
f
keV to
f
MeV. The latter type of
accelerators, such as the cyclotron, the linac, and the synchrotron, cover higher energy
region from
f
MeV to
f
GeV.
Flexibility in ionic species, energy, intensity, time structure, beam spot size, etc., are
the most essential characteristics common to all the accelerators used for ion beam ap-
plications. The TIARA facility is unique in its design specialized for the ion beam appli-
cations, especially to materials science and to biotechnology. Agreat variety of ionic species
from proton through bismuth is available through four types of accelerators: a K110 AVF
cyclotron, a 3-MV tandem accelerator, a 3-MV single-ended accelerator, and a 400-kV ion
implanter [14,15]. The energy range covered by the four accelerators is shown in Fig. 5. A
cyclotron [16] has the advantages of the diversity of accelerated particles from protons to
heavy ions with mass number of greater than 200, a broad energy range from
f
MeV to
f
GeV, the ability to increase beam intensity up to mA, and compactness for saving space.
An AVF cyclotron [17,18] has a radially increasing magnetic eld to compensate for the
Figure 4 A birds-eye view of the accelerator complex at the TIARA facility of JAERI, Takasaki.
relativistic mass increase for isochronism, and an azimuthally varying eld to provide the
additional vertical focusing. A schematic drawing of the AVF cyclotron is shown in Fig. 6.
Ions generated by the external ion source are axially injected at the center of the AVF
cyclotron. The ions are led to the medium plane of the cyclotron magnet by the electric eld
generated between inector electrodes in the shape of a spiral. The ions make revolutions
periodically in the magnetic eld generated by the cyclotron magnet. The revolution period
of the particles is kept constant to accelerate charged particles using a xed-rf voltage
supplied to the electrodes in the frequency range of MHz. After the ions reach an extraction
radius, the beam trajectory is shifted outward by using the electric eld of a deector,
Figure 6 Schematic drawing of the ion acceleration in the AVF cyclotron.
Figure 5 Energy range of the ion beams available at the TIARA facility of JAERI, Takasaki.
followed by a magnetic channel for weakening the magnetic eld, to extract the ions from
the cyclotron.
Accelerator technologies for the cyclotron have evolved to meet such requirements of
the ion beam as the increases in energy and beam intensity. Precise experiments demand a
cyclotron beamof high quality, namely, high energy and time resolutions. Development of a
at-top acceleration system [19,20] and a beam cooling system [21] resulted in the
minimization of the energy spread in the cyclotron beam. The at-top acceleration
technique is indispensable for the production of a cyclotron microbeam [22]. A highly
stable beam required for the at-top acceleration can be provided by a precise and exible
control of the temperature of the cyclotron magnet yoke.
Quick Change of Ion Species and Energy
Most of beamtimes allocated for ion beamapplications are completed within 24 hr, which is
comparatively shorter than that for nuclear physics. Ordinarily, ion species and energy have
to be changed to collect the necessary data for investigation of dependence on LET in
substances, for example. Such researches require several beam times for data acquisition,
taking users almost a year or more. In case of a cyclotron, more than 2 hr of overall time is
needed for reexcitation of the cyclotron magnet and optimization of the parameters of the
whole systems. The change of the ion beam condition during the individual beam time is
inecient for increasing the rate of cyclotron operation. Quick change of the beam without
loss of time is essential for ecient use of the beam time.
Acocktail beamacceleration method [23] is a smart technique, extremely useful for
quickly changing ion species and energy in the cyclotron. Cocktail ions, consisting of
dierent ion species, having almost identical mass-to-charge ratio (M/Q) produced by the
ECR ion source, are simultaneously injected into the cyclotron. The cyclotron parameters
are optimized for one of the cocktail ions. The selected ion is fully accelerated under the
isochronous condition given by 2pf
rf
/h = ( Q/M)(B
0
/m
0
c
2
), where f
rf
is the rf frequency, h is
an acceleration harmonic number, B
0
is the magnetic eld for isochronism, m
0
is the unied
atomic mass unit, and c is the speed of light. Other ions with slightly dierent M/Q values
are gradually shifted an additional amount in rf phase, and get out of the accelerating phase
of the rf cycle. Other ion species can be extracted fromthe cyclotron by slightly changing the
frequency or the magnetic eld to match the dierence of the M/Q. Changing of the
frequency or the magnetic eld can be completed within a few minutes.
Ion beams are useful to simulate the environment in space, where semiconductor
devices are exposed to high-energy heavy-ion impact. Incorrect operation of semiconductor
devices such as single-event upset results from the heavy-ion irradiation. The cocktail ion
families of M/Q = 4 and 5, available at the JAERI AVF cyclotron facility [24], are
frequently utilized to investigate the tolerance of the semiconductor devices to the radiation,
and to survey highly radiation-tolerant semiconductor devices appearing in the market.
Eciency of the radiation-tolerance testing for thousands of kinds of semiconductor devices
has been totally improved by the cocktail acceleration technique.
3.4. Irradiation of Ions
Simultaneous Irradiation of Dierent Ion Beams
Structural materials for ssion reactors (as well as for future fusion reactors) are being
exposed to intense neutron ux for many years. In the case of fusion reactor, 14-MeV
neutrons, produced by the fusion reaction of d+t !
4
He+n, induce nuclear reactions of
(n, a) and (n, p), while helium and hydrogen gases are accumulated in the reactor mate-
rials. Constituent atoms of the reactor materials are recoiled by the neutrons. The neutron
irradiation causes a degradation of the material properties through displacement of the
constituent atoms, accumulation of the hydrogen and helium gases, and other nuclear
transmutation products.
Development of advanced structural materials for blankets of the fusion reactor is
particularly signicant, because the eciency and life expectancy of the blankets are limited,
respectively, by the operating temperature and the radiation damage of the materials. Prop-
erties of candidate materials such as low-activation ferritic steel and silicon carbide ber-
reinforced silicon carbide (SiC/SiC) composite are being investigated under dual or triple
ion beam irradiation at TIARA facility. A variety of the neutron irradiation conditions in
the reactors can be simulated in a relatively short period by simultaneous irradiation of mul-
tiple ion beams. Especially, triple ion beam irradiation is extremely eective in simulating
the synergistic eect of displacement damage and the heliumand hydrogen accumulation in
the reactor materials. It helps to develop new reactor materials.
Simulation of the neutron-induced damages using triple ion beams is schematically
shown in Fig. 7. Aproton and a heliumion are provided by the ion implanter and the single-
ended accelerator, respectively. Heavy ions, such as iron or silicon, accelerated by the
tandem accelerator, are injected into the target simultaneously. For example, the SiC/SiC
composite was tested under triple ion beam irradiation consisting of a 380-keV proton, a
1.2-MeVheliumion, and a 7.8-MeVSi
3+
ion. The triple irradiation systemis equipped with
an energy degrader and a beam scanner for uniform three-dimensional (3-D) irradiation.
Uniform Irradiation by Beam Scanning
A uniform-irradiation technique is commonly used for ion beam applications in materials
science and biotechnology, and for biomedical application such as cancer therapy. Uni-
formity of the irradiated-particle density distribution is essential to bring about the same
Figure 7 Schematic drawing of the damage in reactor materials induced by neutrons, and its
simulation by the triple-ion-beam irradiation.
irradiation eects in a substance with a large area or with a number of target samples aligned
in several lines. A relative dose variation of at most F10% is maximally tolerable for the
uniform irradiation. Several uniform-irradiation systems have been developed so far to
meet individual demands of ion beam applications. The most economical method for
uniform irradiation is a double-scattering beam delivery using two sets of scatterers [25].
In this system, we should pay attention to the energy loss in the scatterers, a change of a
charge state of the ions, activation of the scatterer material, and production of nuclear
fragments.
Formation of a beam spot with a homogeneous prole by using multipole magnetic
elds is a good way to atten the particle distribution [26]. Multipole elds, such as octupole,
dodecapole, and 16-pole, generate a stronger focusing force for the particles traveling away
from the axis of the multipole, while the focusing force acting on the particles close to the
multipole axis is comparatively weak. The nal particle distribution is highly dependent on
initial beam size and angular spread. A very careful designing of the multipole magnet and
the beam transport system is required to obtain a uniform particle distribution with a hard
edge at an irradiation point.
A 2-D beam scanning system equipped with a set of magnets or electrostatic plates to
deect the beamhorizontally and vertically is commonly used for uniformirradiation over a
large area, e.g., >10 10 cm
2
. A schematic drawing of the 2-D beam scanning method is
shown in Fig. 8. The scanning area may be varied by changing the excitation currents of the
Figure 8 Schematic drawing of the two-dimensional beam scanning system using a set of magnets
to deect the beam horizontally and vertically.
deection magnet or the voltages supplied to the electrostatic plates. By using a raster beam
scanning system [27], a large rectangular area can be irradiated with continuously delivered
particles. The beam-sweeping speed and the spacing between neighboring trajectories are
kept constant. Uniformity of the particle distribution is determined by beam spot size and
trajectory spacing. The raster beam scanning system is utilized for estimating damage in
solar cells from exposure to high-energy protons and for inducing mutation in plants by
heavy ions.
A wobbler beam delivery system [28], another 2-D beam scanning system, is used
typically for biomedical applications. Abeamis circularly wobbled at several dierent radii
to form a uniformdose distribution in an area up to 30 cm in diameter. The beam-sweeping
speed at the outer wobble radii increases, since the horizontal and vertical deection
frequencies are constant. When beam intensity remains constant, longer irradiation time
makes up for a deciency of particle density in outer wobbles to achieve a uniformradiation
eld. A continuous uniform irradiation over a round area can be realized by a spiral beam
scanning method [29]. The beam-sweeping speed is kept constant even for larger radii, while
the trajectory spacing in a radial direction is invariable. Precise control of the irradiation
time is unnecessary for the spiral beam scanning system.
3.5. Microbeam
Superiority of the Microbeam
Spatial andtargeting resolutions of the ion irradiation in a nite area are greatly enhanced by
using a microbeamwith a beamspot size of 1 Amin diameter. More precise microanalysis of
elements included in substances is feasible by combining the nuclear microprobe with
analytical techniques like PIXE, NRA, and ion channeling [30]. In recent years, the micro-
analysis technique has become widespread in the eld of life sciences [31]. The microbeam
has also been applied to material processing and to elucidation of radiation eects caused by
high-LET irradiation such as single-event upset of semiconductor devices used in space.
Ahigh-energy ion has higher LETin substances than do electrons or gamma rays with
the same energy. A heavy-ion microbeam with energy of hundreds of MeV is extremely
useful for research in biology and biotechnology as a ne probe for investigation of cell
response and as a specic tool for cell surgery. Asingle ion can cause great damage locally to
a part of the DNA without destroying the whole cell. The microbeam technology is
indispensable for research in the state-of-the-art bioscience, for example, in the investigation
of cell-to-cell communications like bystander eects, the analysis of cellular spatial sen-
sitivity, the interaction of damages caused by individual irradiation, the cellular repair dy-
namics, and in such an intracellular process as apoptosis.
Production of the Microbeam
The rst microbeam was generated by using a Russian quadruplet lens conguration in the
early 1970s at Harwell in Britain [32]. In recent years, microbeam technology has made
remarkable progress to fulll the requirements for several kinds of microprobe analyses.
Nowadays, more than 200 facilities, at which microbeams with energy greater than several
hundreds of keV/nucleon can be provided, are available worldwide for a variety of research
elds.
Beamcollimation using a microaperture foil with a hole of 5 to 10 Amin diameter or a
precisely manufactured slit is an easy method for the microbeam production [33,34]. The
minimum beam spot size was limited to around 5 Am due to the size of the microaperture
and contamination of particles scattered at the edge of the microaperture.
Beam focusing using a multiplet of quadrupole lenses [30,31] is a sophisticated
technique to reduce the beam size to less than 5 Am. A schematic diagram of the focusing
system for microbeam production is shown in Fig. 9. The object of the primary beam is
limited by the rst slit, followed by a series of second slits used for divergence dening and
for beam collimation. An image of these slits can be projected at a focal plane by means of
the focusing lenses. The microbeam size is determined by the demagnication factor of the
lens system. Spherical and chromatic aberrations in the lens system are also taken into
account to minimize the beam size on the basis of the classical optical theory for charged
particles [35].
Microbeam Systems at the TIARA Facility
Three microbeamsystems were developed at the TIARAfacility for application to materials
science and biotechnology. Aheavy-ion microbeamsysteminstalled on a beamline of the 3-
MV tandem accelerator is the rst one developed to study single-event upset (SEU) of
semiconductor devices used for space [36]. The microbeam system can focus heavy-ion
beams such as a 15-MeVnickel ion with a spot size of less than 1 Am. In order to observe the
SEUphenomena at a specic position of the microdevice, the microbeamsystemis equipped
with a single-ion hit system, consisting of single-ion detectors and a fast beam switcher.
A light-ion microbeam system connected with the 3-MV single-ended accelerator was
developed for high-resolution ion beam microanalysis [37]. The highest spatial resolution
of 0.25 Am was achieved for 2-MeV proton and helium ions. The beam spot size was
estimated from the intensity distribution of the secondary electrons emitted from a silicon
relief pattern irradiated with the 2-MeV helium ion microbeam as shown in Fig. 10.
PIXE analysis using the microbeam has an overwhelming advantage in visualizing
very small quantities of elements with a very high sensitivity. For example, 2-D distribution
of small amounts of elements included in cells can be obtained by the micro-PIXE tech-
nique. An in-air micro-PIXE system using a light-ion microbeam was developed at the 3-
MV single-ended accelerator facility [38]. A schematic diagram of the in-air micro-PIXE
system is shown in Fig. 11. A proton microbeam with spatial and targeting resolutions of
1 Ampenetrates a 4-Am-thick Mylar lm, used as a sample backing and a vacuumpartition,
Figure 9 Schematic diagram of the focusing system for the microbeam formation.
Figure 11 Schematic diagram of the in-air micro-PIXE system.
Figure 10 Estimation of the spot size of the 2-MeV helium ion microbeam from the image of a
silicon relief pattern obtained by detecting secondary electrons.
and it is delivered to an experimental sample mounted on an annular sample holder in the
atmosphere. The X-rays emitted from the elements bombarded by the incident proton are
measured by a Ge or Si(Li) detector placed near the sample. The microbeam is scanned
horizontally and vertically to obtain 2-D element distribution. The elemental species is
identied by the X-ray energy. The in-air micro-PIXE system enables multielemental
mapping of samples in atmospheric environment, which avoids drying the samples.
Formation of the submicron microbeam contributes enormously to the enhancement of
spatial resolution in the micro-PIXE analysis. The micro-PIXE analysis technique is widely
applied to various research elds such as biomedical research, dentistry, environmental
science, and geology.
For living-cell irradiation using high-energy heavy ions, a vertical microbeamline was
developed at the JAERI AVF cyclotron facility. Asingle-ion hit technique was also applied
to the microbeam system to irradiate the specic part of individual cells with a single ion
[33,34]. Heavy ions accelerated up to hundreds of MeV are transferred to the end of the
beam line and delivered to the atmosphere through the microaperture with an inner
diameter of 10 Am. A sample stage is placed just after the microaperture. The positioning
accuracy of the sample stage relative to the microaperture is better than 1 Am. Single ions
are detected with a plastic scintillation counter placed downstream of the sample stage.
Every time a single ion is detected, the ion injection into the cyclotron is inhibited by kick-
ing out the ion beam with a beam switcher installed on the injection line until the single-
ion detection system and a data processing system become ready for the next single-ion
event.
Commissioning of a newmicrobeamsystemis in progress to improve the resolution of
the high-energy heavy-ion microbeam. The new microbeam system has been installed on
another vertical beam line of the JAERI AVF cyclotron. A schematic diagram of the
microbeamsystemis shown in Fig. 12. The spot size of hundreds of MeVheavy-ion beams is
expected to be reduced to less than 1 Am by using a quadruplet of quadrupole lenses in
combination with a series of slits. The microbeam system is also equipped with a single-ion
hit system.
3.6. Future Prospects of the Ion Beam Technologies
The research and technology elds of the ion beam applications will continue to expand
hereafter. Further development of the ion beam technologies is indispensable for the prog-
ress of the state-of-the-art research and technology. For example, ion beams with nano-
meter or subnanometer size are expected to be applied to the processing of materials with
hyperne structure and 3-D nanoanalysis. Pinpoint targeting of ions at a base of DNA on
nanometer scale will bring a breakthrough in biotechnology, especially for plant breeding.
A remarkable progress in biotechnology and in materials science is envisaged by the
applications of heavy ions with energy of more than 100 MeV/nucleon. Relative biological
eectiveness (RBE) in plant cells is enhanced in the LETrange from200 to 300 keV/Am. The
GeVheavy ions provide suitable range and LET for plant breeding to generate useful plants
such as UV-resistant crops, disease-resistant crops, insect-resistant crops, and environment-
remediable plants. The GeV heavy ions can make an almost straight hole along their paths
in an organic lm with a very high aspect ratio. The lm will be used to develop newly
functioned devices such as a precise lter for selecting atoms and molecules and an organic
semiconductor device with which ultrafast data processing may be possible. The heavy-ion
beam will also be useful for a radiation test of fabricated semiconductor devices in an
atmospheric condition to simulate single-event phenomena in space.
4. APPLICATIONS TO SPACE AND MATERIAL SCIENCE
AND ENGINEERING
Using ion beam technologies denoted in Section 27.3, research and development of
advanced materials and devices have been made for their space, nuclear, and industrial
applications. As typical examples of such researches, evaluation and development of semi-
conductor devices for space application, characterization of radiation degradation of nu-
clear materials, beamanalysis and modication of inorganic materials, and beamprocessing
of organic materials are described in this section.
4.1. Evaluation and Development of Semiconductors Used in Space
Articial satellites, which are now used for communication, broadcast, weather forecast,
etc., are equipped with a variety of semiconductor devices, which are often exposed to the
high levels of radiation found in space. Such energetic particles, called cosmic rays, cause
the degradation and malfunction of semiconductor devices, which lowers both the mission
lifetime and reliability of satellites. Using ion beam irradiation facilities at TIARA, which
have been uniquely adapted for simulating the radiation environment of space, we have
Figure 12 Schematic diagram of the high-energy heavy-ion microbeam system using a quadruplet
of quadrupole lenses and slits. The focusing-type microbeam apparatus is combined with the single-
ion hit system, similar to the existing single-ion hit system installed in the collimation-type micro-
beam apparatus.
been examining and characterizing the radiation resistance of semiconductor devices
intended for space applications. Radiation eects on semiconductor devices have been
investigated to clarify the mechanisms of radiation-induced degradation, and as a result, to
propose a way for developing better radiation-hard devices.
Radiation Degradation of Solar Cells
For an example of evaluating radiation degradation of semiconductor devices, the irradi-
ation test results of silicon (Si) and gallium arsenide (GaAs) solar cells using protons and
electrons are shown here. Solar cells, which are the main power sources for articial satel-
lites, are degraded predominantly by high-energy protons and electrons in space because
the existence probability of such particles is high in their mission trajectories such as the
geostationary orbit. Their degradation results from the introduction of displacement
damage in semiconductors, and thus, control of irradiation parameters of charged particles
such as uniformity of beam ux is important for detailed analysis of radiation tolerance of
solar cells. In the tests using a proton beamaccelerated at 10 MeVwith AVFcyclotron, solar
cell samples were irradiated uniformly in an area of 10 10 cm
2
with a magnetic beam
scanner. In irradiation of protons at energies from 1 to 6 MeV using a tandem accelerator,
the beamscan area was 4 4 cm
2
. In both cases, the nonuniformity of the irradiation uence
was kept within 3%. Electron irradiation of 1 MeV to solar cells was also performed by
using Cockcraft-Walton-type or Dynamitron Cascade-type accelerator at JAERI. The
performance of solar cells was examined under illumination of pseudosunlight at zero air
mass (AM0) condition before and after irradiation, or during irradiation by using simulta-
neous irradiation technique of charged particles and pseudosunlight [39].
Figure 13 shows typical results of the degradation of crystalline Si solar cells having
a back surface eld and reector structure (Si-BSFR), which were qualied by National
Space Development Agency of Japan (NASDA) for space usage, when irradiated by 10-
MeVprotons and 1-MeVelectrons. The pn junction of the cell samples, with a size of 2 cm
2 cm 50 Am, was fabricated by phosphorus (P) doping to a depth of 0.15 Am into boron
Figure 13 Dependence on 10-MeV-proton and 1-MeV-electron uence of the remaining factor of
short circuit current (I
sc
) for Si-BSFR solar cells. Circles and squares represent the results for
samples irradiated with 10-MeV protons and 1-MeV electrons, respectively. Broken lines represent
the tting results based on a model mentioned in the text.
(B)-doped, p-type substrate with a resistivity of 10 V cm. As shown in Fig. 13, which is a
gure of the electrical performance of solar cells, normalized short-circuit current I
sc
decreased with increasing uence up to 1 10
13
/cm
2
for proton irradiation and 1 10
16
/
cm
2
for electron irradiation. The logarithmic degradation observed in such uence ranges is
explained by the conventional model, i.e., a decrease in the minority carrier lifetime [40].
Over these uences, we found an anomalous change in I
sc
, i.e., I
sc
recovered about 5% to
10%, and abruptly dropped to nearly zero at proton uences around 1 10
14
/cm
2
and
electron uences around 1 10
17
/cm
2
. The conventional model cannot account for this
anomalous phenomenon. Based on an analysis of all the results obtained, the following
model was proposed: The hole concentration in the p-type substrate decreases owing to the
introduction of lattice defects, which act as hole traps. It raises the Fermi level of the
substrate corresponding to a change in the electrical properties of the substrate from p-type
to intrinsic. Thus, the depletion layer extends toward the backside of the solar cell, which
enhances the eciency of carrier collection and consequently the I
sc
recovers. When the cells
are irradiated further, minority-carrier mobility in the depletion region decreases and thus a
rapid decrease in drift length takes place. As the drift length becomes shorter than the width
of the depletion layer, electrons generated by light illumination do not reach the pn junction,
leading to I
sc
=0. Simulation results using the model are also shown by broken lines in Fig.
13, indicating that the experimental data are well described by the proposed model [39].
Based on the model described above, the degradation of Si solar cells equipped in a
Japanese articial satellite ETS-6 has been predicted. The result is illustrated in Fig. 14.
Actual ight data are also plotted in the gure. It should be noted that the obtained data are
in good agreement with prediction, indicating high reliability of the method. The results
obtained in this research have been summarized in Handbook of Si Solar Cells for Space
Application [41], which is used as an important database on space Si solar cells developed in
Japan. In addition, both junction-type Si solar cells with high radiation resistance have been
developed from these results [42].
GaAs solar cells have also been evaluated at TIARA because in 1998 the articial
satellite COMETS, which was equipped with similar cells, orbited across a strong ionization
Figure 14 Prediction (solid line) and actual ight data (squares) of the degradation of Si solar cells
equipped in ETS-6.
radiation environment called the van Allen belt due to its incorrect positioning. The char-
acterization of proton and electron irradiated cells has been used to predict the total lifetime
of the COMETS satellite. This has contributed to a revision of the COMETS initial mission
program. On the basis of those experiences, at present we have been studying radiation
eects on newtypes of solar cells, such as InGaP/GaAs/Ge triple-junction solar cells. It was
found from those investigations that the improvement of radiation resistance of GaAs
middle cells is a key issue for developing higher radiation resistant InGaP/GaAs/Ge solar
cells [43].
Radiation-Induced Malfunction in Electronic Devices
In contrast to the radiation degradation of solar cells, malfunction called SEU is caused by
irradiation of energetic particles into large-scale integrated circuits (LSIs) such as highly
integrated memory devices. Because a malfunction of electronic devices is regarded as one of
the most serious problems in space, the evaluation of single-event tolerance of LSIs is
indispensable for their space applications. It is well known that SEUs are triggered by the
generation of a high concentration of charge (highly dense electronhole plasma) in
semiconductors due to impingement of a heavy ion. The probability of SEU depends on
the LET of an ion in a device substrate, typically Si, because the value of charge generated in
semiconductors is proportional to LET. For accurate examination of SEUs taking place in
an LSI by a single ion, a special apparatus has been designed and installed in TIARA. By
using the apparatus, high-energy heavy ions accelerated by AVF cyclotron irradiate sample
devices at low uence rates, e.g., several hundreds of ions per second. We also used cocktail
beams developed in TIARA to make SEU tests eciently. Details of cocktail ion beams
have been described in the previous section.
Typical results obtained for the 256-kbit static random access memories (SRAMs),
which were developed for space application by NASDA, are shown in Fig. 15. The SEU
cross section increased with LET in a range above a threshold value and reached a constant
Figure 15 Single-event upset cross section for 256-kbit SRAM as a function of LET. Closed circles
and solid line represent experimental and tting results, respectively.
value called the saturated cross section. The threshold LET and the saturated cross sec-
tion can be related to the critical charge necessary to cause SEU and to the size of memory
cells, respectively. It was determined from those tests that the threshold LET and the sat-
urated cross section were 6.4 MeV/mg/cm
2
and 3.2 10
8
cm
2
, respectively, for the 256-kbit
SRAM. Here the threshold LET is dened as the LET value corresponding to one hun-
dredth of the saturated cross section. Using these values, the SEU tolerance for the devices
in space have been estimated. As a result, it was deduced that SEU occurs approximately
once a week in the geostationary orbit, showing its strong radiation resistance sucient for
space application. Based on results obtained at TIARA, radiation-hard devices like 1Mgate
arrays have been newly developed for components used in articial satellites [44].
Because SEU occurs when the amount of electric charge collected in a memory cell
exceeds a critical value, an understanding of the transportation of charges induced in mem-
ory devices by ion irradiation is indispensable to clarify the mechanism of SEU. For this
purpose, a microbeam irradiation system was designed and installed in a beam line con-
nected tothe tandemaccelerator. Details of the microbeamsystemhave beendescribedinthe
previous section. To measure transient currents in several nanoseconds, a wide-bandwidth
measurement systemwith a charge sensitivity of 20 fCand a temporal resolution of 10 ps was
developed. The developed system is schematically illustrated in Fig. 16. Using the system,
charge collection behaviors for several kinds of devices such as Si pn junction diodes, GaAs
Schottky diodes, etc., have been examined. Typical results obtained for silicon-on-insulator
(SOI) devices are described below [45].
For the development of SEU-hardened memory devices, it is expedient to reduce
charge collected in a memory cell. For this purpose, the formation of buried oxide in device
structures, i.e., the fabrication of SOI structure, is considered a useful method because such
a buried oxide layer can be expected to suppress the charge collection due to the drift and
funneling processes. However, no experimental approach had been made for the charge
collection in SOI devices. To investigate the charge collection in the SOI structure, transient
currents induced in SOI pn junctions by heavy ions such as 15-MeV carbon (C) or oxygen
(O) ions have been measured.
The samples were pn junction diodes formed on an SOI wafer fabricated by wafer
bonding technique. The thicknesses of the n-type top Si layer with resistivity of 24 V cm,
the oxide layer, and the n-type Si substrate with resistivity of 150 V cm are 5.7, 0.48, and
630 Am, respectively. The p region, which is 50 Am in diameter and 0.5 Am in depth, was
Figure 16 Schematic drawing of the system developed for transient current measurement using
heavy-ion microbeam.
formed by diusion of B. The sample diodes were mounted on a chip carrier with 50-V
double-ended microstriplines. They were irradiated with 15-MeVCor 15-MeVOions using
a heavy-ion microbeam, and transient currents induced in the sample diodes by ion
irradiation were monitored using a 50-GHz wideband sampling oscilloscope and a super-
conducting delay line, which were connected with the p contacts.
Figure 17 shows the transient currents induced in the SOI pn junction diode irradiated
with 15-MeV C ions when the reverse bias applied to the junction was 10 V. The result
obtained for the bulk Si pn junction diode when the reverse bias was 10 Vis also displayed in
Fig. 17 for comparison. The values of currents obtained for the SOI sample were shown to be
lower than those for the bulk Si diode. The amount of charge collected in the p region can be
derived fromtime integration of the obtained transient currents. For the SOI diode, the total
amount of collectedcharges was estimatedto be 210 fC, which was approximately one half of
that obtained for the bulk Si diode (470 fC). The lowvalues of collected charges in the SOI pn
junction can be interpreted as the only charges generated in the top Si layer reach to the p
region, i.e., the buried oxide suspends the charge conduction arising from the tunneling
eect.
The amount of positive charge created in a depletion region can be estimated
theoretically by using the length of a depletion layer, the value of LET for incident ions,
and the ion energy necessary to produce an electronhole pair in Si (3.6 eV). Assuming that
all positive charges generated in the top Si layer of the SOI device by ion irradiation were
transferred to the p contact, the amount of collected charge was estimated to be 260 fC. The
total amount of collected charge obtained from transient currents in the SOI device was
comparable with the estimated value. It indicates that the charge collection in the SOI pn
junction is limited in the top Si layer, whereas the penetration depth of 15-MeV C ions
(about 14 Am) is much deeper than the top Si layer. Similar results were also obtained for 15-
MeV O ion irradiation. All the above ndings demonstrate that the SOI structure has a
strong SEU resistance, and therefore they are suitable for the application to electronic
components used in space.
Figure 17 Transient current induced in SOI pn junction diode by 15-MeV C-ion irradiation (solid
line). The result obtained for bulk Si pn diode is also shown as a dotted line in the gure for
comparison. The reverse bias of 10 V was applied to pn diodes during measurements.
Development of Radiation-Resistant SiC Devices
Silicon carbide is regarded as a promising material for electronic devices used in space due to
its outstanding electrical properties [46] and excellent radiation resistance [47]. For its
application to highly integrated devices, it is indispensable to establish a selective doping
technique of electrically active (donor and acceptor) impurities. Because diusion technique
cannot be employed due to the extremely low diusion coecients of impurities in SiC, ion
implantation is the most promising way to dope impurities in selective regions of SiC.
For the electrical activation of implanted impurities, removal of defects by post-
implantation annealing is required. Whereas doping of high concentration of donors or
acceptors is necessary to produce low resistive regions, amorphous SiC layers subjected to
high-dose implantation at room temperature (RT) can hardly be recovered by postim-
plantation annealing. In this case, hot implantation is expected to be eective for avoiding
amorphization of ion-implanted SiC, because induced defects are partially removed during
implantation. The inuence of hot implantation on the electrical activation of P donors in
SiC have been investigated [48]. Fourfold implantation of P ions at 80, 100, 150, and 200
keVwas performed for p-type SiCwith a net acceptor concentration of 4 10
15
/cm
3
to form
a box prole of P atoms with a mean concentration of 1 10
18
to 5 10
19
/cm
3
and a depth
0.25 Am. Implantation temperature was altered in the range from RT to 1200jC. After
implantation, the samples were annealed in an Ar ambient up to 1500jC for 20 min. Ohmic
contacts were formed by A1 deposition on the P-implanted layers. The electrical properties
of the samples were examined by Hall measurements using van der Pauw method.
Figure 18 shows the carrier (electron) concentration in SiC samples implanted with
P at 5 10
19
/cm
3
at RT or 1200jC as a function of annealing temperature. The carrier
concentrations measured at RT are plotted in this gure. The carrier concentration for both
samples increased with annealing temperature. This indicates an increase of electrical
activation of P and a decrease of residual defects due to annealing. As for the comparison
between RT and 1200jC implantations, samples implanted at RT showed lower carrier
concentration as compared to samples implanted at 1200jCat every annealing temperature.
Since, in this sample, an amorphous layer was produced by implantation, such a highly
defective layer is thought to remain even after 1500jC annealing, which causes poor elec-
Figure 18 Free carrier (electron) concentration in SiCsamples implanted with P ions at RT (circles)
and 1200jC (squares) as a function of annealing temperature. Annealing was performed for 20 min in
Ar atmosphere. The electron concentration was obtained from Hall eect measurement at RT.
trical activation of implanted P atoms. The relationship between implanted P concentration
and implantation temperature has been investigated to clarify optimum condition of P
doping. It was found that the eects on hot implantation enhanced with increasing im-
planted P concentration, and the optimumimplantation temperature depends on implanted
P concentration [48]. For example, for high-dose P implantation, the highest carrier concen-
tration was obtained in samples implanted at 800jC. In addition, from positron annihila-
tion spectroscopy (PAS) study, this result can be explained in terms of the migration and
formation of vacancy defects due to annealing [49].
In fabrication of p-type SiC, doping of acceptors such as B and aluminum (Al) is one
of the key issues because their electrical activation ratio (atoms activated electrically/
implanted atoms) was not high enough even when hot-implantation technique was adopted.
It was reported that B and Al atoms located at Si sublattice sites act as shallow acceptors in
SiC[50]. In addition, the incorporation of Band Al in SiCcould be controlled by the change
in Si/C ratio during epitaxial growth of SiC [51]. From these ndings, the introduction of
additional C atoms by implantation, called C coimplantation, is expected to enhance the
electrical activation of acceptors. The eects of Ccoimplantation on the electrical activation
of Al and B acceptors in SiC have been investigated. It was found that the electrical prop-
erties of B- and A-implanted SiC are improved by C co-implantation [52,53]. In this study,
n-type 4H-SiC samples with a net donor concentration of 5.3 10
15
/cm
3
were used. The
samples were implanted with B ions at RT. Abox prole of B with a mean concentration of
5 10
18
/cm
3
and a depth of 0.5 Am was achieved by conducting a vefold implantation.
Prior to the implantation of B, a vefold implantation of C or Si ions was performed at RT
or 800jC to form a similar box prole to that of B. After implantation, samples were an-
nealed at 1630jC for 30 min in a SiC crucible in pure Ar ambient. Ohmic contacts were
formed using the deposition of Al and subsequent sintering at 950jC for 3 min in vacuum.
Hall measurements were carried out in a temperature range from 180 to 700 K using a van
der Pauw arrangement.
Figure 19 shows the free hole concentration as a function of reciprocal temperature for
the samples implanted with B, co-implanted with C and B (C/B) and co-implanted with Si
Figure 19 Free hole concentration as a function of reciprocal temperature for B- (triangles), C/B-
(circles), and C/Si-implanted (squares) SiC. Solid lines represent the tting results.
and B (Si/B). The ionization energy was determined from the slope of these curves (solid
lines in the gure) to be equal to 285 meV, which agrees with the B ionization energy in 4H-
SiC [54]. This indicates that implanted B species are activated electrically in all these
samples. The free hole concentration was found to increase by the C coimplantation and to
decrease by the Si coimplantaion. The hole concentration at RT in samples coimplanted
with C at 800jC and B was approximately 7.1 times as high as that in the sample implanted
with only B. Considering that hole concentration at RT in samples coimplanted with C at
RT and B was approximately 4.1 times as high as that in the sample implanted with only B
[52]; the results obtained indicate that hot coimplantation of C is quite eective for im-
proving the electrical properties of B acceptors. A similar increase in the free hole con-
centration due to Ccoimplantation was also obtained for Al acceptors in SiC [53,55]. It was
also observed that the intensity of the PL peak at 383.9 nm, which arises from shallow B
acceptors, increased by C coimplantation. In addition, the value of the D
II
center, which is
related to C interstitials, increased by coimplantation of C. These results are interpreted in
terms of a site competition eect and/or an alternation of the degree of compensation. In
conclusion, the C coimplantation technique is quite eective to form p-type layers in SiC.
Oxidation for forming insulator on SiC is also one of the key issues for the fabrication
process of SiC devices. The relationship between the oxidation process and the electrical
characteristics of SiC metaloxidesemiconductor eld eect transistors (MOSFETs) have
been studied [56,57]. A photograph of the enhancement-type SiC MOSFETs fabricated in
this study is shown in Fig. 20. The source and drain regions of the MOSFETs were formed
using P hot implantation mentioned above. In this study, oxide on SiC was formed by
pyrogenic oxidation (a wet oxidation process using direct reaction between hydrogen and
oxygen gases) and subsequent thermal treatment in steam or H
2
atmosphere. Details of the
fabrication process of the MOSFETare described in Ref. [57]. Fromthis study, it was found
that the postoxidation annealing methods can improve the channel mobility of SiC
MOSFETs, which is one of the most important characteristics, although the obtained
value was only 30% of the ideal value. Furthermore, the radiation response of the SiC
MOSFETs has been examined. It was found that SiCMOSFETs showed approximately 100
times higher radiation resistance than Si MOSFETs. [58,59].
Figure 20 Photograph of the enhancement-type SiC MOSFET.
4.2. Characterization of Radiation Degradation of Nuclear Materials
The investigation of radiation degradation of materials used in nuclear fusion reactors as
well as ssion reactors is indispensable for their safety and long-term operation with a high
reliability. In fusion reactors, structural materials, solid tritium breeder materials, and
insulating ceramic materials will be exposed to fast (14 MeV) neutrons generated via DT
reactions in high-density plasma. When reactor materials are irradiated with such fast
neutrons, heavy displacement damage as well as He and H atoms, which are produced by
transmutation reactions like (n, p) and (n) are introduced into the materials.
The Development of Triple-Beam Irradiation Apparatus
In order to develop materials for fusion reactors, it is important to investigate synergistic
eects of displacement damage and transmutation-induced gas products on their physical
and mechanical properties. For this purpose, a triple-beam irradiation apparatus has been
designed and installed at TIARA. Aphotograph of the triple-beam irradiation apparatus is
shown in Fig. 21. Using the apparatus connected with a 3-MV tandem accelerator, a 3-MV
single-end accelerator, anda 400-kVion implanter, three species of ions, e.g., heavy ions, He,
and H can be simultaneously irradiated into samples for simulating the radiation environ-
ment of a fusion reactor. Each beam line has an angle of 15j from the other beam line, and
three kinds of beams are focused on the target sample in a vacuum chamber. Besides, for
wide-area irradiation with high uniformity, a beam scanning system is also installed in each
line. Since Al foils are installed for energy degradation in the irradiation chamber, the
penetration depth of irradiated ions can be adjusted. The temperature of samples is also
controllable from 80 to 1300 K. Details of the apparatus were described elsewhere [60].
Austenitic Steel, Ferritic/Martensitic Steel, and Vanadium Alloy
Using the triple-ion beam irradiation apparatus, the microstructural evolution of austenitic
stainless steel, which is considered as a structural material for water-cooled fusion reactors
Figure 21 Photograph of the triple-beam irradiation apparatus.
such as the international thermonuclear experimental reactor (ITER) has been investigated
[61,62]. The austenitic stainless steel samples with a composition of Fe16Ni14Cr0.25Ti
2.5Mo in wt.%were irradiated simultaneously with 12-MeVNi, 1-MeVHe, and 350-keVH
ions in a temperature range between 300j and 400jC. The irradiated samples were observed
by transmission electron microscopy (TEM), and the number density of dislocation loops in
the irradiated region was studied.
Figure 22 shows the depth distribution of the number density of dislocation loops for
the sample irradiated with 12-MeV Ni, 1-MeV He, and 350-keV H triple-ion beams. The
number density of dislocation loops decreases in a region between 1.0 and 1.5 Am. It was
reported that hydrogen interacts with dislocation in steels at a relatively low temperature
[63]. Considering that the estimated projection range of He and Husing TRIMis around 1.5
Am, the results obtained in this study suggest that the generation of dislocation loops is
suppressed by the interaction of defects and He and/or H. In addition, very small cavities
whose average diameter and density were 1.4 nmand 1.5 10
24
/cm
3
respectively were found
in the triple-beam-irradiated region. Since such high-density small cavities were not
observed in a region irradiated with only 12-MeV Ni ions, the creation of high-density
small cavities is thought to be an eect of simultaneous irradiation of Ni, He, and H.
Sekimura et al. [64] reported that high-density small cavities (diameter: 10 nm, density: 10
21
/
cm
3
) were created in austenitic stainless steel samples implanted with dual beams of Al and
He ions. Therefore, the creation of small cavities is one of the synergistic eects of
displacement damage and transmutation-induced gas products. The growth of the cavities
in F82 was also obtained in the region irradiated with triple beams. The growth strongly
depends on heat and mechanical treatment process [65]. Since such a growth relates to
microhardness and leads to swelling of the steel, this nding is considered very important for
the predicted lifetime of steels. Besides, the remarkable swelling for pure vanadium (V) and
V alloys, which are also candidates for fusion materials due to triple-beam irradiation, was
found [66]. Because this swelling could not be attributed to single-or/and dual-beam
irradiation, this also can be concluded to be synergistic eects.
SiC/SiC Composites and Other Materials
Ceramic matrix composites are expected to be applied to structural materials for fusion
reactors because of their excellent mechanical properties at high temperature and their
Figure 22 Depth distribution of the number density of dislocation loops for austenitic stainless
steels irradiated with 12-MeV Ni, 1-MeV He, and 350-keV H triple beams.
noncatastrophic failure behavior. SiC/SiC composite materials are regarded as one of the
attractive candidates for fusion materials. In addition to the excellent mechanical properties
as ceramics, SiC/SiC materials have an advantage of low residual radioactivity. The eects
of triple-beam irradiation on SiC/SiC materials are described below. SiC-ber-reinforced
SiC-matrix (SiCf/SiC) composites and a monolithic SiC(h-SiC) were used in this study [67].
The samples were irradiated with triple beams (6-MeV Si
2+
, 1.2-MeV He
+
and 250-keV
H
+
ions) at 1000jC. As a result of TEM observation, He bubbles and cracks were found in
SiC matrix, and the number of He bubbles and cracks strongly depended on the fabrication
process of SiC/SiC composites. The size of the bubbles also depended on the fabrication
process of SiC/SiC composites. The turbostratic carbon structure was formed in the carbon
interphase layer due to irradiation, although the interphase layer was the nongraphitic
carbon structure before irradiation. Furthermore, a new crystalline SiCphase was observed
in the carbon interphase irradiated with Si ions. Details of irradiation eects on SiC/SiC
composites are described in Refs. [6769].
In addition to SiC/SiC, irradiation eects on insulators such as Al
2
O
3
were also
examined [70]. As a result, synergistic eects such as the diusion of H and the growth of
cavities were observed in samples irradiated with triple beams. As for carbon ber com-
posites, the microhardness increased by triple-beam irradiation [71], which was a dierent
result from that obtained from 14-MeV neutron irradiation (8 10
19
n/cm
2
) experiment.
4.3. Beam Analysis and Modification of Inorganic Materials
Applying ion beams, surface-sensitive analysis and modication in atomic and electronic
structures of inorganic materials have been developed. Ion beam modication of titanium
dioxide (TiO
2
), carbon-based materials, and the analysis of Nb/Cu multilayers and VO
2
using ion beam are described as follows.
Modication of the Characteristics of TiO
2
Titanium dioxide has many attractive characteristics for photoactive applications, such as
photocatalytic coatings and dye-sensitized solar cells. However, its large optical bandgap
(3.03.2 eV) is a disadvantage taking into account the utilization of sunlight. Doping TiO
2
with dierent impurities using ion implantation is known to provide an eective modica-
tion of its electronic structures, thereby improving the separation of the photogenerated
electronhole pairs and/or extending the wavelength range of the TiO
2
photoresponse into
the visible region [72]. Therefore, the eects of uorine (F) and chromium (Cr) implanta-
tions on the characteristics of TiO
2
have been taken up [7375].
First, the results of F implantation into TiO
2
will be described. Single-crystalline TiO
2
rutile with a h001i crystallographic axis was implanted with 200-keV F ions at a uence
range from1 10
16
to 1 10
17
/cm
2
and subsequently annealed in air. The radiation damage
and its annealing behavior were investigated by Rutherford backscattering spectrometry in
channeling geometry (RBS/C) and PAS. X-ray photoelectron spectroscopy measurements
conrmed the occupation of F atoms on O-lattice sites in the outermost region of the
implanted surface layer. Secondary ion mass spectrometry (SIMS) was employed
for probing F distribution in the as-implanted and post-annealed samples. The electronic
structures of the F-doped TiO
2
were also evaluated by theoretical calculations to predict the
doping eect on the spectral response of TiO
2
[74].
The disorder peaks in RBS/C spectra lessened during isochronal thermal treatment.
This can be attributed to a columnar regrowth within the total thickness of the damaged
layer [76]. The pronounced recovery in the Ti and O sublattices was achieved by such a
recrystallization process due to annealing up to 1200jC. PAS study revealed that the crystal
structure was recovered by the migration of vacancy-type defects to the surface. According
to the SIMS results shown in Fig. 23, the F depth prole was shifted to a shallower region
along with the damage recovery and this resulted in the formation of the F-doped layer
where the impurity concentration steadily increased toward the surface. Importantly, this
method enabled F atoms to be introduced in a controlled manner at specic locations to
realize impurity concentration gradients in TiO
2
. From the ab initio band calculations, it
was found that the F doping caused a modication of the electronic structure around the
lower edge of the conduction band. This probably leads to a reduction in the eective
bandgap energy, in other words, to an improved optical response in the visible-light region.
The uorination of TiO
2
surfaces would enhance their chemical and optical stabilities and
open avenues toward photoelectronic materials with various applications. In this sense, F
ions have the possibility of acting as promising dopants in a TiO
2
photocatalyst.
The surface charge separation eciency was characterized using photo-induced
transient charge separation (PITCS) measurement proposed by JAERI [77]. By this
technique, the total number of photocarriers transported toward the surface can be
estimated as a function of illuminated photon energy without disturbing the spontaneous
surface band bending, because of contactless observation under no-applied bias. The PITCS
measurements were carried out for studying hole generation in TiO
2
. The samples used in
this study were TiO
2
rutile lms. The samples were implanted with Cr ions at 150 keV at a
dose of 5.0 10
15
ions/cm
2
and subsequently annealed at 600jC for 5 hr in air. For
comparison, uniformly Cr-doped TiO
2
rutile lms, highly oriented undoped TiO
2
anatase,
and TiO
2
rutile lms were also examined. Figure 24 shows the incident-photon-energy
dependence of the surface charge separation eciency of the samples [75]. The vertical axis
represents the ratios of the number of surface transported holes (h
+
) to the number of
induced photons. An increase in charge separation eciency for samples implanted with Cr
ions, and subsequently annealed, was observed, especially around 350 nm, as compared to
other samples. The total number of h
+
for Cr implanted lm was estimated to be
approximately 15 times higher than that for TiO
2
anatase. The obtained result suggests
that the charge separation properties are improved by making a gradient of Cr distribution.
Figure 23 Depth prole of F in TiO
2
rutile single crystals implanted with 200-keV F ions. (a) As-
implanted, (b) 600jC-annealed, and (c) 1200jC-annealed samples.
Carbon-Based Materials
In the research and development of inorganic materials, the formation mechanism and
thermal stability of carbon-based materials have been intensively investigated. The for-
mation processes of carbon onions (graphitic spheres) and nanocapsules in copper and gold
have been elucidated through simultaneous TEM observation under C-ion irradiation [78].
This apparatus consists of two sets of accelerators and a TEM. One of the accelerators is a
400-kV ion implanter at TIARA, which can accelerate more than 30 kinds of elements
including high-melting-point metals. The other one is a duoplasmatron ion source with
accelerating voltage of 40 kV. In this apparatus, the following techniques are available as
well as conventional transmission electron microscopy: high-resolution electron micro-
scopy, scanning electron microscopy, scanning transmission electron microscopy, CCD
camera and video-recording system and electron energy loss spectroscopy. For the
observation of C onions, copper (Cu) plates were implanted with C ions at temperatures
from300j to 700jC. The high-magnication micrograph of Conions is shown in Fig. 25. As
a result of TEMobservation during Cion irradiation, it was found that the accumulation of
C atoms above 1020 at.% (i.e., >1 10
17
C/cm
2
) and high enough temperature for the
migration of C atoms are needed for creating a nucleus of C onions in Cu plates. The
production rate of C onions using ion implantation was 6 to 8 times higher than that using
electron irradiation. Furthermore, the creation of C onions and nanocapsules was found to
depend on the quality of substrate materials. Details of this study are described in Ref. [79].
In addition to C onions, C atoms condense into various kinds of chemically bonded
forms, and they are known to have excellent physical properties depending on the bonding
nature. This means that research and applications not only in the materials science but also
in other scientic elds are expected. At JAERI, the optimum growth conditions have been
successfully obtained for the preparation of high-quality C
60
, diamondlike carbon, and
nanocrystalline diamond by means of ion-beam-assisted deposition [8082]. The suscept-
ibility of Ni/C
60
thin lms to thermal treatment, the formation of nanocrystalline diamond
and nanotubes due to codeposition of Co and C
60
, and the surface modication of glassy
Figure 24 Incident photon energy dependence of the surface charge separation eciency (h
+
/
photon) measured by PITCS. Squares, circles, triangles, and diamonds represent the results obtained
for Cr-implanted rutile, Cr-doped rutile, undoped rutile, and anatase TiO
2
lms, respectively.
carbon by hydrogen doping have also been characterized [8386]. In the following, materials
synthesized from C and C
60
are described as examples.
Ion beam deposition (IBD) was carried out by employing an acceleratordecelerator
system under ultrahigh vacuum. In this study,
12
C
+
ions were used as source, and Si(111)
and Ir(100)/MgO(100) single crystalline were used as substrates [87]. The typical ion beam
conditions were in the energy range of 50200 eVand in the beamcurrent around 1 mA. On
the other hand, as for the ion-beam-assisted deposition (IBAD) experiments, a special
chamber was designed. In the chamber, three dierent sources (C
60
, Ne ions, and transition
metals) can be installed. In the case of evaporating C
60
molecules, energetic Ne
+
ions were
also introduced in an energy range up to 5 keV. Ne
+
ion beamwas obliquely incident at 60j
relative to the surface normal. In the case of using ions with high Z element, the sputtering
eect should be considered during irradiation. The chamber can be evacuated up to 1.2
10
6
Pa, and the vacuum was kept at less than 5 10
5
Pa during IBAD experiments.
As a result of IBD and IBAD experiments [80], nanodiamonds immersed in the
dominant sp
3
amorphous carbon lms were found. Patterns were formed via the dynamical
process between the sputtering and the deposition eects [82]. Hexagonal nanosized
diamonds were also prepared from the C
60
vapor with the simultaneous irradiation of
1.5-keV Ne
+
ions at a temperature of 700jC. Furthermore, although C and iridium (Ir) are
immiscible, defects introduced by Cimplantation could favor the supersaturated Catoms in
the subsurface region. Fig. 26 shows an atomic force microscope (AFM) micrograph of
diamondlike carbon (DLC) lm on Ir(100) prepared by IBD method (100-eV
12
C
+
)
followed by thermal annealing at 600jC under He gas environment. After annealing,
DLC lm suered from blistering because of immiscibility between C and Ir. One can
recognize a symmetric, owerlike pattern of blistering with a needlelike dot at the center.
Figure 25 High-magnication micrograph of C onions.
The petals correspond to the bumps in blistering and the centered dot has been conrmed
to be nanodiamond by micro-Raman spectroscopic analysis. The growth from the
nucleated embryos was enhanced by a heat treatment. These results suggest that the
nucleation sites can be controlled by using ion beam technique. Therefore, it is concluded
that nanopattern as well as materials with interesting features may be synthesized by using
ion beam irradiation technique with changing ion energies and substrate temperature.
Study of Materials by Ion Beam Analysis
Ion beamanalysis performed on materials synthesized at TIARAis described in this section.
Multilayers in which dierent thin metal lms are stacked alternatively are considered as a
mirror material reecting short wavelength lights such as soft X-rays. To form high-quality
mirror materials, it is indispensable to measure the thickness of lms and the atness of the
lminterfaces. Niobium(Nb) lms deposited on single-crystal a-Al
2
O
3
, MgOsubstrates by
electron beamevaporation technique has been investigated by RBS/Cand X-ray diraction
analyses. Figure 27 shows 2.7-MeV
4
He
+
RBS spectra from Nb on a-Al
2
O
3
substrate
measured under random conditions and the h110i aligned conditions. As a result, it was
found that some amount of disorder exists around the interface region between Nb layer
and a-Al
2
O
3
substrate [88]. From the fact that the ratio of the h110i to random spectrum
yield from Nb lm is 0.044 at just behind surface peak, the excellent crystallinity of the lm
was conrmed. Multilayers consisting of Nd and Cu lms have also been examined to
understand the relationship between crystallinity and the fabrication process [89].
15
N
nuclear reaction analysis (
15
N NRA) was conducted using
15
N ions accelerated by 3-MeV
tandem accelerator in this study. Since
15
N NRA can detect small amounts of residual
hydrogen existing at the interface between Nb and Cu layers, the thickness of each layer can
be estimated. The results obtained from
15
N NRA are shown in Fig. 28. The calculated
result is also shown as a solid line in the gure. From the comparison between experimental
and calculated results, the optimum condition of the fabrication of the multilayers was
determined. Details are described in Refs. [88,89].
Figure 26 AFM micrograph of DLC lm on Ir(100) prepared by IBD method (100 eV
12
C
+
),
followed by thermal annealing at 600jC under He gas environment. After annealing, DLC lm
suered from blistering because of immiscibility between C and Ir. Size of the micrograph is 9.85
9.85 Am
2
.
The fabrication process of vanadium oxide (VO
2
) has also been studied using RBS/C.
Since optical and electrical properties of VO
2
are dramatically changed at 68jCdue to phase
transition, VO
2
is regarded as one of the candidates for thermally activated electronic or
optical switching devices for optical bers or sensors. To obtain the desired properties, the
development of the fabrication process for very thin lms, without crystalline defects on
various substrates, is required. Single-crystalline VO
2
thin lms on (0001) plane of a
sapphire substrate have been synthesized by a laser ablation method. The quality of VO
2
was examined by X-ray diraction and RBS/C method. The electrical resistance and the
optical transmittance of the VO
2
lm were measured under increasing and decreasing
temperatures. At a temperature of 68jC, an abrupt transition of resistance from metal to
Figure 27 RBS/C spectra of 2.7-MeV-
4
He
+
from Nb(110) epitaxial lm on a-Al
2
O
3
substrate [Nb
(140 nm)/Cu (42 nm)/Nb (48 nm)/a-Al
2
O
3
]. The 100-nm-thick Nb lms were fabricated at 750jC by
electron beam evaporation.
Figure 28 Hydrogen distribution observed in Nb/Cu multilayers by
15
N NRA (circles). The tting
result (solid line) is also shown in the gure. The structure of Nb/Cu multilayers is Nb (2 nm)/Cu/Nb
(5 nm)/Cu/Nb (10 nm)/Cu/Nb (20 nm)/a-Al
2
O
3
, where the thickness of Cu layer is 20 nm.
insulator was observed [90]. In addition, as a result of the study of Mo doping eects,
transition temperature was found to decrease with increasing Mo concentration [91].
4.4. Beam Processing of Organic Materials
Irradiation of heavy ions like Au and Kr deposits a heavy damage along the ion track in
polymer lms. When some polymer lms are irradiated with heavy ions and dipped in an
alkaline aqueous solution, micropores are produced along the ion track. Since the shape and
size of pores of polymers can be controlled by etching conditions and by the species of heavy
ions, these polymer lms are expected to be used for high-performance lters and ion
detectors [92]. The development of the polymer lters and ion detectors are described as
follows.
Thermoresponsive Polymer Films
Polymer lms that have useful functions such as selective transportation and absorption of
specic molecules are expected to be applied for high-performance lters used in medicine
and biology. The fabrication process of polymer lms with pores using heavy-ion irradi-
ation consists of the following four steps: (1) the preparation of a thin core lm, (2)
irradiation of heavy ions into the core lm, (3) the treatment of the core lm in an alkaline
solution, and (4) grafting of a polymer, which changes the shape responsive to temperature.
In this study [92], a copolymer consisting of diethylene glycol diallyl carbonate (DEBA) and
acryloyl-L-proline methyl ester (A-ProOMe) was used as the core lm. DEBA acts as a
comonomer with high sensitivity to ion beam irradiation, and A-ProOMe enhances the
anity to the polymers that are subsequently grafted. The core lms were irradiated with
84
Kr ions at 6.19 MeV/n at a uence of 10
7
/cm
2
. After irradiation, the lms were treated in
an aqueous 6 M NaOH solution at 60jC for 1 hr to make pores 1.3 Am in diameter. Then,
the lms were immersed in an aqueous A-ProOMe solution, and irradiated with gamma
rays at a dose of 30 kGy for grafting. A-ProOMe is a cross-linkable polymer to give a
temperature-responsive hydrogel. Thus, its volume increases by absorption of water belowa
critical temperature (14jC). The volume of swelled A-ProOMe is about 400 times larger
than nonswelled one. The diameter of cylindrical pores was 0.7 Amat 30jC. Figure 29 shows
the temperature dependence of the permeability of p-nitrophenol for A-ProOMe grafted
lms. No signicant change of the permeability was observed in temperature ranges below
12jC. However, a remarkable increase in permeability was found above 14jC, which
corresponds to the lower critical solution temperature. It is noteworthy that molecules can
be selectively separated by changing the volume of the grafted polymers in the cylindrical
pore, which are regulated by the change in temperature. Furthermore, when N-isopropy-
lacrylamide (NIPAAm) was used as a responsive material grafted on lms, polyethylene
glycol molecules with the same mass could be separated from polyethylene glycol with a
dierent mass by controlling temperatures, as shown in Fig. 30.
Ion Detectors Based on CR39
Polyallyl diglycol carbonate (CR39) is well known as a plastic track detector [93]. However,
the sensitivity of a plastic detector to ion irradiation should be greater compared to that of
CR39 for detection of lighter ion particles with higher energy, when the ion detectors are
applied to the eld of cosmic ray physics, nuclear physics, space radiation, and neutron
dosimetries. Therefore, The development of a newplastic track detector based on CR39 that
shows high sensitivity to proton beams are described next.
Several types of CR39 copolymers containing 13 wt.% of N-isopropylacrylamide
(NIPAAm) and 0.01 wt.% of Naugard 445 were prepared by cast polymerization. The
copolymerizations were performed with 3% diisopropyl peroxydicarbonate (IPP) as an
initiator at 70jC for 24 hr to give copolymer lms (CR39/NIPAAm). Details of the
fabrication process of CR39/NIPAAm are described in Ref. [94]. Protons at an energy of
10 MeV were incident onto CR39/NIPAAm. The eects of NaOH concentration and
temperature of an etchant to ion beam sensitivity of CR39/NIPAAm were investigated.
Results for CR39/NIPAAm show a broad maximum of sensitivity at 5 N NaOH at 70jC.
Figure 29 Temperature dependence of the permeability of p-nitrophenol for A-ProOMe grafted
lms. The permeability (P) was calculated from the equation, P=jV/AC, where j, V, A, and C are
the slope of the permeationtime curve, the volume of the receiver chamber, the surface area of the
membrane, and the concentration of p-nitropenol in the donor chamber, respectively.
Figure 30 Temperature dependence of the permeability (P) of polyethylene glycol molecules for
N-isopropylacrylamide (NIPAAm) grafted lms. Polyethylene glycol with four kinds of masses (1
10
2
, 110
3
, 210
3
, 710
4
) are contained in the solution.
For the comparison between CR39 and CR39/NIPAAm, the sensitivity of CR/NIPAm to
ion particles was much higher than that for CR39 in LET ranges below10 keV/Am[94]. This
indicates that CR/NIPAAm is very useful for an ion particle detector.
5. APPLICATIONS TO BIOLOGICAL SCIENCE
5.1. Mutagenesis in Plants
Introduction and Irradiation Methods
Since the discovery of mutation induction by X-rays in maize [95], numerous studies on
plant mutagenesis by ionizing radiation have been carried out. The biological eect of ion
beams was also investigated and it was found that ion beams show high RBE of lethality,
mutation, and so on compared with low-LET radiation such as gamma rays, X-rays, and
electrons [96,97]. Because ion beams deposit high energy on a target densely and locally, as
opposed to low-LET radiation, it is suggested that ion beams predominantly induce single-
or double-strand DNA breaks with damaged end groups whose reparability would be low
[98]. Therefore, it seems plausible that ion beams can frequently produce large DNA
alteration such as inversion, translocation, and large deletion rather than point mutation,
resulting in producing characteristic mutants induced by ion beams. However, the charac-
teristics of ion beams on the mutation induction have not yet been clearly elucidated.
As the rst facility of ion beams for biological and material use, TIARA was
established in 1991. The characteristics of ion beams for the biological eects and the
induction of mutation have been investigated using model plants, Arabidopsis, chrysanthe-
mum, tobacco, wheat, and so on. Several kinds of ion beams such as C, He, Ne, and Ar were
experimentedon in this study and mostly 220-MeVCions were used. All ions were generated
by the AVFcyclotron in TIARA. The physical properties of the 220-MeVcarbon ions are as
follows: Incident energy at the target surface was 17.4 MeV/u, mean LET in a target (0.25-
mm thickness) was estimated to be 110 keV/Am as water equivalent, and the range of ions
was ca. 1.0 mm. These physical properties were calculated by ELOSS code program, a
modied OSCAR code program [99]. Particle uences of the ions were determined using a
diethyleneglycol-bis-allylcarbonate (CR39) lm track detector. Electron beams (2 MeV;
JAERI, Takasaki, Japan) were also used as a low-LET ionizing radiation control.
In general, ion beams were scanned at more than 50 50 mm, and exited the vacuum
chamber through the beam window made of a 30-Am-thick titanium foil. The irradiation
sample was placed in the air at a distance of 10 cm from the beam window. In the case of
Arabidopsis or tobacco seeds, for example, 1003000 seeds were sandwiched between
kapton lms (7.5-Am thickness) to make a monolayer of the seeds for homogeneous ir-
radiation. In the case of rice or barley seeds, the embryo side was kept facing toward ion
beams, whereas for calli or explants in a petri dish, the lid of the petri dish was replaced with
a kapton-lm cover to decrease the loss of the energy of ion beams. Samples were irradiated
for less than 3 min for all doses.
Biological Eects of Ion Beams
Determination of biological eects of ion beams is an inevitable problemfor the application
of ion beams to mutagenesis in plants. In the previous investigations, it was shown that RBE
for growth inhibition and so on reached a peak at around 72174 [100] or 190 keV/Am[101],
suggesting LET dependence of RBE of higher plants is similar to that of mammalian cells.
However, in these experiments, the Bragg peak was adjusted on the target and/or only a few
LETs were investigated. To acquire more detailed data on biological eects by using
penetrating ions with various kinds of LET, several investigations have been carried out in
TIARA [102106]. Most eorts were focused on LET dependence of survival and other
endpoints of ion beams in the case of plant seeds. In general, all the experiments showed that
the RBE peak of survival and other endpoints was around ca. 230 keV/Am and more (Fig.
31). By using carbon ions with dierent LET, Hase et al. [106] indicated that the RBE for
survival and chromosome aberration in tobacco increased with increasing LET and showed
the highest value at 230 keV/Am. Shikazono et al. [105] found that the highest LET of the
peak RBE for lethality of Arabidopsis was around 221 keV/Am for carbon ions and around
350 keV/Am and more for neon and argon ions. Therefore, it is almost certain that the LET
having a maximum of RBE for lethality is higher in plant seeds than in mammalian cells.
Mutation Rate
In order to compare mutation frequency induced by 220-MeV Cions with that by low-LET
radiation (electrons), Arabidopsis visible phenotype loci were chosen as follows: transparent
testa (tt) whose seed coat is transparent because of lack of pigment; glaborous (gl), which
have no hair on their leaves and stems; and long hypocotyl (hy) whose hypocotyl is longer
than that of the wild type in the light condition. Mutation frequencies of tt, gl, and hy
induced by carbon ions were 8- to 34-fold higher than those by electrons (Table 2). In this
study, irradiation doses for the induction of mutation were determined from the RBE of
carbon ions compared with that of electrons on the survival of plants, which was
approximately 5. Both doses are at three-quarters of the shoulder dose of each survival
curve [104].
Mutation Spectrum
It is necessary to compare the mutation spectruminduced by ion beams with that by the low-
LETradiation to gure out a special feature of ion beams as an eective mutagen. Mutation
Figure 31 The relative biological eectiveness (RBE) of lethality as a function of linear energy
transfer (LET). (From Refs. 105 and 106.)
spectrumwas rst investigated on the ower color of chrysanthemumcv. Taihei (pink color)
by Nagatomi et al. [107]. The explants of leaf and oral petals incubated in agar medium
were irradiated with carbon ions of 220 MeV. After irradiation, the culture was transferred
to a new medium to induce callus. The mutation induction of the regenerated plants from
the callus was investigated, comparing the results with those with gamma-ray irradiation.
The mutation rates of ower color induced by ion beams were approximately half of those
induced by gamma rays in both oral petal and leaf. Most ower color mutants induced by
gamma rays were light pink, and a few were dark pink (Table 3). On the other hand, ower
mutants induced by ion beams showed complex and stripe types other than single color
(Fig. 32). The complex-type ower color mutants increased as the dose of ion beams rose.
The color spectrum of the ion-beam-induced mutants shifted from pink to yellow. Those
specic mutants such as complex and striped color types have never been obtained by gam-
ma-ray irradiation in the cultivar. Thus, mutation spectrum of ower color induced by ion
beams is wide and novel mutation phenotypes can be induced.
Recently, mutation spectrum of ower color and ower shape of carnation was also
investigated by Okamura et al. [108]. In the carnation variety Vital (spray-type, cherry pink
owers with frilly petals) tested, ower color mutants such as pink, white, and red were
obtained by X-ray irradiation, whereas the color spectrum of the mutants obtained by
carbon ion irradiation was wide such as pink, light pink, salmon, red, yellow, and complex
and striped types. Furthermore, many kinds of round shape of petals were induced in
addition to ower colors. These indicate that ion beams can induce novel ower color and
shape with high frequency.
Novel Mutants
Until now, several new mutants were induced by ion beams. Representative mutants will be
described below.
Table 2 Mutation Frequency Induced by Carbon Ions and Electrons
Mutagen (dose) Locus
Mutation frequency/locus/diploid
cell/dose (Gy) ( 10
6
)
Carbon ions (150 Gy) tt 2.3 (34-fold)
a
gl 1.7 (8)
Hy 2.0 (16)
Electrons (750 Gy) Tt 0.068
gl 0.21
hy 0.12
a
Compared to the frequency of the electrons.
Table 3 Mutation Spectrum of Flower Color in Chrysanthemum
Mutagen
Mutation frequency (%)
White Light pink Dark pink Orange Yellow Complex/Stripe
Unirradiated 0 0.3 0 0 0 0
Gamma rays 0 27.7 2.1 0 0 0
Carbon ions 0.3 4.6 0.3 0.3 0.2 10.2
Original variety Taihei with pink owers was used.
Arabidopsis as a Model Plant. In an attempt to isolate novel mutants by means of
ion beams, Arabidopsis [Arabidopsis thaliana (L.) Heynh.] was used as a model plant. This is
because thousands of mutants were already induced in Arabidopsis by using chemical
mutagens, X-rays, T-DNA mutagemesis, etc. Therefore, if a novel mutant phenotype is
discovered by using ion beams, it would be well grounded that ion beams are a powerful tool
as a new mutagen. As one of such a mutant phenotype, UV-B-resistant plants were chosen,
because many UV-B-sensitive mutants have been isolated in Arabidopsis but there has been
no report of mutants in any higher plants that are resistant to UV-B light. Four UV-B-
resistant mutants [ultraviolet-light insensitive (uvi) 14] have been isolated in 5100 M
2
fam-
ilies derived from carbon-ion-irradiated 1280 M
1
seeds. The fresh weight of uvi1, uvi2 and
uvi4, after 1 month under UV-B radiation, was 2-fold higher than that of wild type, and 1.5-
fold higher in the uvi3 (Fig. 32). Especially, uvi1 showed very great ability of both photo-
reactivation and dark repair. The reduction of CPD and (6-4) photoproducts that are two
major DNA damages caused by UV-B are both faster in uvi1 than in wild type, indicating
that uvi1 mutation would gain the DNA reparability [109].
New anthocyanin-accumulated or -defective mutants were also isolated. A new
mutant, anthocyanin spotted testa (ast), which has the spotted pigmentation on the seed
coat, has been isolated from 11,960 M
2
plants derived from 1488 self-pollinated M
1
.
Anthocyanin content was about 6 times higher at 6 days after owering than that of the
wild-type seeds [110]. Two new loci of anthocyanin-defective tt phenotype (tentatively ttA,
ttB) have been found along with the research of mutation frequency experiment (unpub-
lished data). Both genes seem to encode enzymes of anthocyanin biosynthetic pathway. On
the other hand, a novel ower mutant, frl1, has serrated petals and sepals, but the other
oral and vegetative organs appear to be normal (Fig. 32). FRL1 gene should act in petal
and sepal development in an organ-identity-specic manner [111].
Other Plants. As already described in Mutation Spectrum, complex and striped
types of ower color have been obtained in chrysanthemum. A higher mutation frequency
Figure 32 Novel mutants induced by ion beams. Top left: 1-month-old plants of Arabidopsis wild
type (top) and UV-B-resistant mutants (bottom) under high UV-B (1113 kJ/m
2
/day) condition. Top
center and right: complex (center) and striped (right) ower-color varieties of chrysanthemum.
Bottom left: ower of Arabidopsis frl1 mutant. Bottom center and right: new carnation varieties with
round petals (center) and Dianthus type petals (right).
of complex ower color mutants were derived from oral petal irradiation than that from
leaf irradiation [107]. Also, many kinds of ower color such as pink, light pink, salmon, red,
yellow, complex and striped types, and various kinds of round petals were induced fromthe
carnation variety Vital [108] (Fig. 32).
In order to develop an ecient procedure for obtaining a desired mutation, ion beams
were applied to tobacco anthers, and potato virus Y (PVY)-resistant mutants have been
selected. A high frequency (2.93.9%) of resistant mutants was obtained by the irradiation
of C and He ions with a dose of 510 Gy [112,113].
Two mutant lines of yellow mosaic virus resistant barley were found in ca. 50,000 M
2
families. The character of the resistance in a eld was not changed over three generations
[114].
High eciency of getting blast-resistant mutants of rice was also obtained using ion
beams, although resistant mutants were already obtained by gamma rays and by thermal
neutrons [115].
Molecular Mechanisms of Mutation
In order to investigate the DNA alteration of mutations induced by ion beams in plants,
polymerase chain reaction (PCR) and sequencing analysis was performed to compare DNA
fragments amplied from carbon-ion- and electron-induced Arabidopsis mutants [116,117].
Fourteen out of 30 loci possessed intragenic mutation (small mutation) such as point
mutation or deletion of several to hundreds of bases. For comparison, 16 out of 30 loci
possessed intergenic mutation (large mutation), such as chromosomal inversion, trans-
location, and total deletion covering their own loci. These results imply that in the case of
mutation induced by ion beams, half of the mutants have intragenic small mutation and the
other half have large DNA alteration such as inversion, translocation, and large deletion
(Table 4). In such an alteration, a common feature was that all the DNA strand breaks
induced by carbon ions were found to be rejoined using short homologies [117]. These
results suggest that the nonhomologous end joining pathway operates after plant cells are
exposed to ion beams.
Conclusion
The uvi1uvi4 mutants were induced from 1280 M
1
, and the ast and frl1 mutants were
obtained from the ospring of 1488 M
1
seeds. As ion beams showed high induction of
mutation of the known loci such as tt, gl, hy, it would be true that ion beams can highly
induce not only known mutants but also novel mutants. In chrysanthemum and/or
carnation, complex and striped ower color and new ower-shape mutants that have never
been induced by low-LET radiation have been produced, indicating that ion beams could
induce various kinds of mutants on the similar phenotypes. In conclusion, the character-
Table 4 Classication of Mutation Induced by Carbon Ions
Intragenic mutation
(point mutation, small deletion, etc.)
Large DNA structural alteration
Inversion
translocation
Total
deletion
47% 40% 13%
istics of ion beams for the mutation induction are (1) to induce mutants with high frequency,
(2) to show broad mutation spectrum, and (3) to produce novel mutants. For these reasons,
chemical mutagens such as EMS and low-LET ionizing radiation such as gamma rays and
electrons will predominantly induce many but small modications or DNA damages on the
DNA strands, producing several pointlike mutations on the genome. On the contrary, ion
beams as a high-LET ionizing radiation will cause few but large and irreparable DNA
damages locally, producing a limited number of null mutations (Fig. 33).
5.2. Cross Incompatibility
In plant breeding, obtaining interspecic hybrid is important for introducing desirable genes
from wild species to cultivated species. However, it is very dicult to obtain a viable hybrid
plant between widely related species. These problems would predominantly come from
sexual reproduction such as cross incompatibility, hybrid inviability, etc [118,119].
The wild species of tobacco, Nicotiana gossei, has been reported to be resistant to more
diseases and insects than other Nicotiana species, several attempts to hybridize it with N.
tabacum (cultivar) have been made. In N. gossei crossed with N. tabacum, it was easy to get
hybrid seeds with conventional cross, but the hybrid plants cannot survive. To overcome the
cross incompatibility, mature pollen from N. tabacum cv. Bright Yellow 4 were irradiated
with helium ions from a tandem accelerator (6 MeV). Two viable hybrid plants were
obtained at the rate of 1.1 10
3
. Both the hybrids were resistant to tobacco mosaic virus
and aphid although the degree of resistance varied. With varying energy and kinds of ions,
hybrid production rate ranged from 10
3
to 10
2
[120122]. The highest rate, 3.6 10
2
,
was obtained with 10 Gy of 100-MeV He ion beams. In the case of gamma irradiation, the
rate of producing hybrids was 3.7 10
5
. Thus, ion beams are powerful tools to overcome
the hybrid incompatibility.
Figure 33 Characteristics of energy transfer of ion beams for mutation induction.
5.3. Gene Transfer
Agrobacterium-mediated DNA transfer technique and direct gene transfer into protoplasts
on the basis of the electroporation technique have frequently been used for the gene transfer
methods in plants. However, these methods were hardly adapted to monocotyledonous
plants or to varieties in which regeneration system was not established. These deciencies
found in gene transfer techniques will be largely overcome if pollen could be used as a DNA
vector.
Penetration-controlled irradiation with ion beams for biological study has been
established [123]. When dry pollens were exposed to He or C ions with shallow penetration
depth (e.g., 4-Am depth in the case of He ions), leaky pollen, which was thought to be a
physical lesion in the pollen envelop induced by ion beams, was eciently produced. Using
this penetration-controlled irradiation system, the transient exogenous GUS expression was
observed at a high frequency (55.1%) when tobacco pollen was incubated in a DNA
solution, following ion beam irradiation of pollen at the penetration depth of 4 Am [124].
The GUS expression frequency increased with the irradiation dose, indicating that the
foreign DNA can be eciently introduced into pollen [125]. However, any transformant
cannot be found in more than 10,000 seeds obtained from the crosses using the DNA
introduced pollen. It is thought that the pollen transformation is dicult only by raising the
transient GUS expression frequency and that the nature of the pollen, such as bimembrane
structure and DNA incorporation capability, may be a fundamental problem in a pollen
transformation system [126].
5.4. Application of Microbeams
Aheavy-ion microbeamprovides a unique way to control the number of particles traversing
individual cells and localization of dose within the cell. A collimated heavy-ion microbeam
apparatus has been installed in a beam line from the AVF cyclotron to develop a novel cell
surgery technique [127] (Fig. 34) (Table 5).
Functional Analysis of Animal Development
As a functional analysis of animal development, an accurate fate map was carried out using
the silkworm, Bombyx mori [128]. Among the beamsizes tested (60- to 250-Amf), 250-Amf
was adopted for the fate mapping of egg at the cellular blastderm stage. When eggs were ir-
radiated near the anterior, posterior, or dorsal periphery, no defective larvae were observed.
A close correlation was observed between the site of irradiation and the site of the defect
induced. Head defects were induced only by irradiation at the anterior half of the egg, where-
as defects in thoracic and abdominal segments were induced by irradiation at the middle and
the posterior part of the egg, respectively. Based on the correlations, a fate map of the B.
mori egg was established [128].
Functional Analysis of Plant Physiology
Microbeamsystemis also very useful for analyzing plant physiology. Root gravitropismis a
simple but wondrously complex phenomenon. Perception of gravity in plant roots has been
well studied, but its signaling fromgravity sensing to physical change of root bending is still
unclear. When primary root apical tissues of Arabidopsis were irradiated by microbeams
with 120-Am diameter, strong inhibition of root elongation and curvature were observed at
root tip. Irradiation of cells that become the lower part of the root cap after gravistimulation
showed strong inhibition of root curvature, whereas irradiation of cells that become the
upper part of the root cap after gravistimulation did not show severe damage in either root
curvature or root growth [129]. These results indicate not only that the root tip cells are the
most sensitive sites for root gravity, but also that the signaling of root gravity would go
through the lower part of the root tip cells after the perception.
5.5. Application of Positron-Emitting Radioisotopes
In plant researches, a real-time imaging system to visualize the movement of various
molecules and ions has been desired for understanding the regulation of plant functions.
The positron-emitting tracer imaging system (PETIS) makes use of positron-emitting nu-
clides and enables the investigator to trace the radioactivity in a plant in real time without
touching the sample plant [130] (Fig. 35). This has been rst realized at TIARA by use of
Figure 34 Schematic diagram of microbeam system for biological study. An ion beam from an
AVF cyclotron is collimated by collimators and a tantalum disk with microaperture with a diameter
of 5250 Am. The collimated ion beam passes through the room air to a target that is set on the
micropositioning stage of an optical microscopic system.
Table 5 Physical Parameters of Heavy-Ion Microbeams
Ions
Specic energy
(MeV/u)
Beam size
(f, Am)
Projectile range
(in water, mm)
LET
a
(keV/Am)
4
He
2+
12.5 40
f
250 1.8 14
f
50
12
C
5+
18.3 10
f
250 1.2 100
f
300
20
Ne
7+
13.0 5
f
250 0.7 400
f
800
40
Ar
13+
11.5 5
f
250 0.24 1200
f
2500
a
LET value on the surface of the target.
cyclotron-produced positron-emitting radioisotopes from which various labeled com-
pounds needed for plant research can be produced. As most positron-emitting radioisotopes
are very short-lived, except for
22
Na, they are produced at the site for experiments using the
PETIS and labeled compounds of nutrients and amino acids (Table 6).
Using the PETIS, real-time [
11
C]methionine translocation was studied for barley. For
the mechanismof Fe uptake in an Fe-decient barley, it was found that leaf methionine does
not participate in the reaction of mugineic acid synthesis, but the methionine produced in
barley roots is used in the biosynthesis of mugineic acid phytosiderophores [131,132].
13
NH
4
+
and H
2
15
O translocation in rice plants were also investigated [133,134]. On the
study of root-nodule functions in common bean, the root site of nitrate uptake and
assimilation was claried by using
13
N-nitrate or ammonium [135]. Furthermore, use of
PETIS and positron-emitting nuclides has given us deep insights into water movement in
living plants [136] and nitrogen (N) distribution in soybean using N-decient and/or N-
sucient plants [137].
Figure 35 Schematic of positron-emitting tracer imaging system (PETIS) and an example of
experimental setup.
Table 6 Production and Application of Positron Emitters in TIARA
Nuclide Half-life Reaction Tracer for experiments on plants
11
C 20 min
14
N(p, a)
11
C
11
CO
2
, [
11
C]methionine
13
N 10 min
16
O(p, a)
13
N
13
NO
2
/
13
NO
3
,
13
NH
4
+
, [
13
N]N
2
18
F 110 min
16
O(a, pn)
18
F
18
O(p, n)
18
F
Aqueous
18
F-, [
18
F]-2-deoxy-2-uoro-
D-glucose,
18
F-proline
48
V 16 days
45
Sc(a, p)
48
V [
48
V]H
2
VO
4
solution
52
Mn 5.6 days
nat
Cr(p, xn)
52
Mn
52
Mn
2+
solution
52
Fe 8.3 hr
nat
Cr(a, xn)
52
Fe
52
Fe
3+
solution
62
Zn 9.2 hr
63
Cr(p, 2n)
62
Zn
62
Zn
2+
solution
5.6. Future Prospects
Ion beams as new mutagen showed breakthrough for the next step of biotechnology by
making new mutants that cannot be obtained by other means. One of the most important
objectives of the postgenome age is to elucidate the function of genes. Unfortunately, it is
very dicult in the plant kingdom to apply the gene-knockout system that was used in
mammals or bacteria. Therefore, ion beams will give us thousands of novel mutants that
inform the function of the mutated gene. On the other hand, microbeam irradiation system
is very useful for research on a cell or cell-to-cell function. If the size of the microbeams are
on the order of several microns or submicrons, accurate and eective irradiation for cell or
chromosome inactivation will be carried out. In researches using a whole plant, behavior of
molecules and ions in a living plant can be analyzed with PETIS. As the problems of
elevated CO
2
concentrations and environmental pollution increase, real-time imaging for
physiological understanding of plants is necessary for the security of food resources and
conservation of the environment.
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Charged Particle and Photon Interactions

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Charged Particle and Photon

Interactions with Matter

ABV [Superexcitation (direct excitation)

Products Ionion recombination

AB Internal conversion and

electron attachment 9:12

B dissociative attachment 9:13

is not due to direct

large numbers of electronic interactions may occur in close proximity.

measured experimentally to the pico-

of 4.0F0.2 [32]. These data are compared with the

that best reproduces the experimentally observed

, with the molecular cation,

, which represents the degradation of the electron energy from

)=4.0 nm; ( ) r(e

)=5.2 nm; ( ) r(e

is shown in Fig. 6 [7782].

is not signicantly involved in the observed intra-track radiation chemistry of pure

scavengers, scavenging reactions may take

. Scavenger systems are commonly used to estimate

in the radiolysis of water. Consequently, understanding the eects of

is important. Fig. 6 compares calculations for several e

, and examination of the details of the IRTcalculations clearly shows

scavenging capacities less than 10

has a statistically (although probably not

increases. The curve for the eect of

. The shift reects the primary role that

on the number of electrons scavenged in aqueous

sbrink, L. J. Electron Spectrosc. Relat. Phenom. 1980, 20, 149.

* are established from electron impact

* (i.e., the value of 1/k

. (From Refs. 10 and 11.)

* (i.e., the resonance

*, whereas its width for the former process is much

and M. Such a situation is depicted

M system is much reduced and even superimposed

in the medium uids. In

(n V4). Similar conclusions have also been reached about

at room temperature correlates with the electron mobility, l

= 0.94 and 0.43

means a shorter mean thermalization range,

changes with mobility, it fails in some cases.

with pressure quite well.

has been measured for three liquids for x-

changes from 0.83 to 0.12 ions/100 eV. The probability of escape is

is very small, 0.005 per 100 eV

), and the solvation energy of the electron

), where the radius of the anion, R

), temperature, and pressure.

for a series of hydrocarbons through the thermalization

[176]. Although the V

B, where AB is a diatomic molecule, may be

state in the FC region and C

potential in the FC region. The

occurs at 11.8 eV and has a lifetime of 2.2 10

, can be considered the unresolved condensed phase equivalent of the

is formed causing an additional peak in the phonon energy-loss tail. The

anion lifetime [118]. For a diatomic molecule with R as the internuclear

, as a function of Ar lm thickness [163] and in Ar/n-hexane double-

resonance reappears in the Ar* desorption yield