6114 J. Phys. Chem.

A 2005, 109, 6114-6127

The Reaction of Phenyl Radical with Molecular Oxygen: A G2M Study of the Potential
Energy Surface

Igor V. Tokmakov,†,| Gap-Sue Kim,‡,¶ Vadim V. Kislov,§,# Alexander M. Mebel,*,§ and

Ming C. Lin*,†
Department of Chemistry, Emory UniVersity, Atlanta, Georgia 30322,Institute of Atomic and Molecular
Sciences, Academia Sinica, P.O. Box 23-166, Taipei 10764, Taiwan, and Department of Chemistry and
Biochemistry, Florida International UniVersity, Miami, Florida 33199
ReceiVed: April 4, 2005

Ab initio G2M calculations have been performed to investigate the potential energy surface for the reaction
of C6H5 with O2. The reaction is shown to start with an exothermic barrierless addition of O2 to the radical
site of C6H5 to produce phenylperoxy (1) and, possibly, 1,2-dioxaspiro[2.5]octadienyl (dioxiranyl, 8) radicals.
Next, 1 loses the terminal oxygen atom to yield the phenoxy + O products (3) or rearranges to 8. The dioxiranyl
can further isomerize to a seven-member ring 2-oxepinyloxy radical (10), which can give rise to various
products including C5H5 + CO2, pyranyl + CO, o-benzoquinone + H, and 2-oxo-2,3-dihydrofuran-4-yl +
C2H2. Once 10 is produced, it is unlikely to go back to 8 and 1, because the barriers separating 10 from the
products are much lower than the reverse barrier from 10 to 8. Thus, the branching ratio of C6H5O + O
against the other products is mostly controlled by the critical transition states between 1 and 3, 1 and 8, and
8 and 10. According to the calculated barriers, the most favorable product channel for the decomposition of
10 is C5H5 + CO2, followed by pyranyl + CO and o-benzoquinone + H. Since C6H5O + O and C5H5 + CO2
are expected to be the major primary products of the C6H5 + O2 reaction and thermal decomposition of
C6H5O leads to C5H5 + CO, cyclopentadienyl radicals are likely to be the major product of phenyl radical
oxidation, and so it results in degradation of the six-member aromatic ring to the five-member cyclopentadienyl
ring. Future multichannel RRKM calculations of reaction rate constants are required to support these conclusions
and to quantify the product branching ratios at various combustion conditions.

Introduction leading to the formation of a phenoxy radical which then can

fragment yielding the C5H5 + CO products above 900 K.5,6
The reaction of phenyl radical (C6H5) with O2 is of great Other minor reaction channels producing H atoms and o- and
importance in the chemistry of incipient soot formation and also p-benzoquinone have also been invoked:7
in combustion of aromatic hydrocarbons, which represent
important ingredients of lead-free gasoline.1-3 At high temper- C6H5 + O2 f o/p-C6H4O2 + H
atures, phenyl radical can be either oxidized through the C6H5
+ O2 reaction or undergoes the polymerization process, C6H5 Under low temperatures, the reaction has been shown to proceed
+ nC2H2 f polyaromatic hydrocarbons (PAHs), which are the by the addition-stabilization process leading to the phenylperoxy
building blocks of soot particles in hydrocarbon combustion1,4 radical (1):8
or subjected to thermal decomposition to smaller fragments. The
competition of these two processes effectively determines the C6H5 + O2 f C6H5OO
amount of soot produced in combustion, and therefore it is
critical to know their mechanisms, rate constants, and relative In addition, theoretical calculations9-12 of the potential energy
product yields under varying combustion conditions, such as surface (PES) for the C6H5O2 system showed that, in principle,
the temperature and pressure. At T g 1000 K, the C6H5 + O2 many other reaction products are also possible:
reaction is believed to occur primarily via the metathetical
C6H5 + O2 f C5H5 + CO2
process
C6H5 + O2 f C5H5O (pyranyl) + CO
C6H5 + O2 f C6H5O + O
C6H5 + O2 f C4H3O2 + C2H2
* Authors to whom correspondence should be addressed. E-mail:
[email protected] (M.C.L.); [email protected] (A.M.M.). To predict reliable reaction rate constants and product
† Emory University.
‡ Academia Sinica.
branching ratios, which can be subsequently used in kinetic
§ Florida International University. modeling of hydrocarbon combustion (oxidation versus incipient
| Present address: University of Missouri-Columbia, Department of soot formation), it is critical to generate an accurate and reliable
Chemistry, 601 S. College Ave., Columbia, MO 65211. PES for the C6H5 + O2 reaction. Although several attempts to
¶ Present address: School of Chemistry, Seoul National University, Seoul
achieve this goal have been made in the recent decade,9-12 the
151-147, Korea.
# Permanent address: Institute of Solution Chemistry of Russian C6H5O2 PESs published so far in the literature are either not
Academy of Sciences, Akademicheskaya St., 1, Ivanovo, 153045, Russia. complete or lack the desired accuracy and reliability. For
10.1021/jp051712k CCC: $30.25 © 2005 American Chemical Society
Published on Web 06/18/2005
Reaction of Phenyl Radical with Molecular Oxygen J. Phys. Chem. A, Vol. 109, No. 27, 2005 6115

instance, Carpenter studied some intermediates and transition where

states for the oxidative cleavage of phenyl radical at the
semiempirical PM3 method.9 Mebel and Lin calculated a variety ∆E(+3df2p) ) E[MP2/6-311+G(3df,2p)] -
of the C6H5O2 isomers10 as well as transition states for the E[MP2/6-311G(d,p)]
C6H5O + O reaction11 using the ab initio PUMP3/6-31G*//UHF/
6-31G* method. However, the use of semiempirical and even and zero-point vibrational energy (ZPE) corrections were
ab initio Hartree-Fock and perturbation-theory-based methods obtained at either B3LYP/6-31G* or B3LYP/6-311++G**
with a moderate basis set may not provide chemical accuracy levels of theory. The higher level correction, ∆E(HLC), was
for such a complicated open-shell system as C6H5O2. The most not actually used because most of the species involved, except
recent theoretical study of the C6H5O2 PES was performed by C6H5 + O2 and C6H5O + O, have the same overall doublet
Fadden et al.12a who employed the hybrid density functional multiplicity and therefore the same number of paired and
B3LYP/6-311+G**//B3LYP/6-31G* method to calculate vari- unpaired electrons. If ∆E(HLC) were included, the relative
ous intermediates and transition states for unimolecular decom- energies of all doublet intermediates, transition states, and
position pathways of phenylperoxy radical. This group also products with respect to the C6H5 + O2 reactants would have
studied in more detail transformations of the key reaction been lowered by ∼3 kcal/mol.15 In the coupled cluster and MP2
intermediate, 2-oxepinyloxy radical,12b and considered the calculations, most of the energies were computed from restricted
mechanism of the 2-oxepinyloxy + O2 reaction.12c The results RCCSD(T) and unrestricted UMP2 components, respectively,
of the DFT calculations may be more accurate than the but in some cases we had to use the unrestricted UCCSD(T)
energetics and molecular parameters calculated earlier, but still, method instead of RCCSD(T) (see Supporting Information).
the accuracy expected from the B3LYP method for the relative RCCSD(T)16 here denotes partially spin-adapted open-shell
energies of intermediates and for the barrier heights is not coupled cluster singles and doubles theory augmented with
sufficient to generate reliable kinetic data, such as rate constants a perturbation correction for triple excitations (the RHF-
and product branching ratios. Moreover, some of the B3LYP RCCSD(T) keyword in the MOLPRO program).
results, for example, the existence of distinct transition states A legitimate question that can be raised is whether the single-
for the C6H5 + O2 f C6H5OO and C6H5OO f C6H5O + O reference coupled cluster method is able to properly describe
reaction steps, do not seem to be qualitatively correct and require the energetics of the C6H5 + O2 reaction system. Although the
further investigation employing higher-level theoretical methods. CCSD(T) level has come to be the gold-standard level of theory
The connections between some transition states and intermedi- for single-reference calculations and it is appropriate for
ates were not unambiguously confirmed by intrinsic reaction calculations of systems with a mild multireference character and
coordinate (IRC) calculations and therefore remain questionable. is certainly more reliable than the DFT B3LYP method, some
Our goal in the present study is to uncover a qualitatively caution in interpretation of the results is warranted in cases when
compelling and comprehensive reaction mechanism (in terms the so-called T1 diagnostic values exceed 0.02.17 As seen in
of the potential energy surface) and to provide chemically Supporting Information, this indeed is the case for some
accurate energetics and molecular parameters for various species intermediates and transition states considered in this work.
involved in the reaction of phenyl radical with O2, which can However, at present, unfortunately, a viable and reliable
be subsequently used in multichannel RRKM calculations of alternative to CCSD(T) calculations does not exist for systems
temperature- and pressure-dependent rate constants for indi- of such size as C6H5 + O2. Multireference CASPT2 or MRCI
vidual reaction steps and for product branching ratios. methods with large and flexible basis sets, which take into
account both nondynamical and dynamical contributions into
electron correlation, are in principle more robust than CCSD(T)
Calculation Methods but only if all valence electrons and valence orbitals are included
into the calculations as part of the active space or at least through
The geometries of various reactants, products, intermediates,
single and double excitations at the post-CASSCF stage.
and transition states in the C6H5 + O2 reaction were initially
Otherwise, these methods suffer from the subjectivity in the
optimized at the hybrid density functional B3LYP/6-31G* level
active space choice and the results appear to be active-space-
of theory13 and their vibrational frequencies were then computed
dependent. The CASPT2 and MRCI energies may be of a rather
using the same method. Because the B3LYP/6-31G* geometries
poor quality if single and double excitations are not included
and frequencies were reported previously for some of the
from all valence electrons (beyond the active space) because a
structures involved,12 we have not recomputed them here; the
large portion of dynamical electron correlation then remains
calculations were performed only for the species that were not
unaccounted for. Ideally, the proper active space for the C6H5O2
considered earlier. For intermediates and transition states
species would include 41 valence electrons distributed over 37
participating in the most important reaction channels, the
orbitals. This huge active space can be reduced to a more
geometries were reoptimized and vibrational frequencies were
reasonable size if one includes only those orbitals that are
recomputed with a larger basis set, at the B3LYP/6-311++G**
involved in particular bond cleavage/bond formation processes
level. All connections between transition states and local minima
and are important for description of nondynamical electron
were confirmed by intrinsic reaction coordinate (IRC) calcula-
correlation; they are usually characterized by the orbital oc-
tions.14
cupation numbers in the CASSCF wave function ranging from
Next, the relative energies of various species were refined 1.98 to 0.02. However, even with a smaller active space, all 41
by single-point calculations using the modified Gaussain 2 valence electrons need to be subjected to single and double
G2M(MP2) method15 with the B3LYP/6-31G* or B3LYP/6- excitations in CASPT2 or MRCI calculations to properly
311++G** optimized geometries. The total G2M(MP2) ener- describe dynamical electron correlation, which, unfortunately,
gies were computed as follows: is unfeasible in the foreseeable future. To evaluate the expected
accuracy of our calculations, we compared our results for C6H5
E[G2M(MP2)] ) E[CCSD(T)/6-311G(d,p)] + + O2 with its smaller analogue, the C2H3 + O2 reaction system,
∆E(+3df2p) + ∆E(HLC) + ZPE for which sensible CASPT2 and MRCI calculations are possible.
6116 J. Phys. Chem. A, Vol. 109, No. 27, 2005 Tokmakov et al.

Figure 1. A graph of possible pathways on the global potential energy surface of the C6H5 + O2 reaction. Relative energies of the reactants,
products, intermediates, and transition states are given in kcal/mol as calculated at the G2M and B3LYP/6-311++G** (in brackets) levels.

CCSD(T) (or G2M) predictions were in a reasonably good Entrance Reaction Channel. The reaction starts with addi-
agreement with MRCI results (on the basis of our limited tion of the oxygen molecule to the radical site of C6H5. As a
comparison) for C2H3O2, which is prototypical of the present result, two different isomers of the C6H5O2 species can be
C6H5O2. An important factor in choosing the CCSD(T) meth- produced, phenylperoxy radical 1 and dioxiranyl radical 8, in
odology is that it can be applied uniformly to study various which the attacked carbon and two oxygen atoms form a three-
transformations on the C6H5O2 PES. Further refinement can be member ring. Let us first consider the formation of the
done in future studies by multireference methods with properly phenylperoxy radical. The well depth at phenylperoxy is
constructed active spaces. T1 diagnostic values are provided as calculated to be 46.3 kcal/mol at the G2M level as compared
indicators of possible importance of multireference effects for to the initial reactants. The B3LYP/6-311+G**//B3LYP/6-31G*
proper description of specific intermediates and transition states. calculation (with B3LYP/6-31G* ZPE) underestimates this value
The calculations were carried out using GAUSSIAN 98,18 by 4.0 kcal/mol. Interestingly, the calculated exothermicity of
Gaussian 03,19 and MOLPRO 200220 quantum chemical pro- the C2H3 + O2 f vinylperoxy radical reaction is rather similar,
gram packages. All optimized geometries (Cartesian coordi- 46.4 and 41.2 kcal/mol at the G2M and B3LYP/6-311G**
nates), moments of inertia, vibrational frequencies, and total levels, respectively.21 At the B3LYP/6-31G* level, Fadden et
and relative energies calculated by different theoretical methods al.12 were able to locate a transition state separating the C6H5
are collected in the Supporting Information.
+ O2 reactants and structure 1. However, single-point B3LYP/
6-311+G**//B3LYP/6-31G* calculations gave the energy of
Results and Discussion that transition state as -0.2 kcal/mol with respect to the
The C6H5 + O2 reaction channels considered in the present reactants, indicating that a barrier on the reaction pathway is
study are illustrated in Figure 1. In our discussion, we mostly not likely to exist. No barrier was found earlier for the related
concentrate on the results, which are qualitatively or quantita- O2 addition to C2H3 to produce the vinylperoxy radical.21 To
tively different from those reported by Fadden et al.12 We investigate more carefully whether a barrier on the C6H5 + O2
analyze various competitive reaction mechanisms with the goal f 1 pathway does or does not exist, we calculated the PES
to select the reaction scheme which includes the most important profile between the reactants and phenylperoxy radical using
channels but is feasible for the upcoming multichannel RRKM partial geometry optimization. In these calculations, the length
calculations of the rate constants and product branching ratios. of the forming C-O bonds was kept fixed at various values
Reaction of Phenyl Radical with Molecular Oxygen J. Phys. Chem. A, Vol. 109, No. 27, 2005 6117

Formation and Decomposition of Phenoxy Radical. After

the phenylperoxy radical 1 is produced, it can undergo a
cleavage of the O-O bond and decompose to the phenoxy
radical, C6H5O, and to the ground-state oxygen atom, O(3P).
The ground electronic state of C6H5O is 2B1 corresponding to
2A′′ if symmetry is reduced to C . Therefore, the overall
s
symmetry of the combined electronic wave function for
separated C6H5O(2B1) + O(3P) within the Cs point group can
be A′ or A′′, if the out-of-plane pz orbital on the oxygen atom
is singly or doubly occupied, respectively. It appears that the
A′ electronic state is more favorable at long (but finite)
separations, and we were able to locate a van der Waals complex
2 between the phenoxy radical and oxygen atom (see Figure
3), which has Cs symmetry and the 2A′ electronic state. At the
G2M level, the complex is bound by merely 1.3 kcal/mol
Figure 2. The C6H5-O2 dissociation potential energy profiles (ZPE relative to C6H5O + O and lies 35.9 kcal/mol higher in energy
corrected, T ) 0 K) calculated using the B3LYP density functional than the intermediate 1. Since the electronic state of the
with the 6-31G* and 6-311++G** basis sets. phenylperoxy radical is 2A′′, the 1 f 2 rearrangement is
symmetry-forbidden and can occur only if symmetry is broken.
from 4.0 to 1.5 Å, while all other geometric parameters were We carefully scanned PES between structures 1 and 2 without
optimized. The partial optimization calculations were performed symmetry constraints using the O-O distance as the fixed
at the B3LYP/6-311++G** level within Cs symmetry where parameter with optimization of all the other internal coordinates.
the symmetry plane contains all atoms in the molecule. Within This was followed by a transition-state search, which resulted
the Cs symmetry point group, both the separated reactants and in TS1-2 shown in Figure 3. As expected, the transition state
intermediate 1 have the same 2A′′ electronic state, so that the has a nonplanar geometry with the departing oxygen atom
O2 addition to the phenyl radical is symmetry-allowed. As seen located somewhat above the C6H5O plane, where the dihedral
from the plot of the potential energy curve against the length OOCC angle τ is -31.9° and -49.4° at the B3LYP/6-31G*
of the forming C-O bond shown in Figure 2, the energy and B3LYP/6-311++G** levels of theory, respectively. The
monotonically and smoothly decreases as the O2 molecule
O-O distance in TS1-2 is also rather sensitive to the basis set
approaches C6H5 until the phenylperoxy radical is produced.
used and decreases from 2.34 to 2.21 Å in going from 6-31G*
This result confirms that no distinct transition state exists on
to 6-311++G**. The optimized structure of the complex 2 is
the C6H5 + O2 f 1 reaction pathway, at least at the level of
less dependent on the basis set, with the O-O distance varying
theory used in the present study. The reaction rate for the O2
only from 2.39 to 2.40 Å. In terms of the O-O bond lengths,
addition will be controlled by a variational transition state, the
TS1-2 is a late transition state in both approximations, but it
position of which and the free-energy barrier will depend on
has a much earlier character with the larger basis set. Meanwhile,
the reaction temperature. We shall discuss the variational
the pathway for the departure of atomic oxygen from the
transition-state structure and energy as well as the rate constant
phenylperoxy radical to form C6H5O is rather peculiar. Initially,
for the O2 addition to the phenyl radical and its temperature
while the IRC path is climbing from intermediate 1 to TS1-2,
dependence in a future study. At this point, we conclude that
the terminal oxygen atom leaves the molecular plane. After the
the C6H5 + O2 f 1 reaction is barrierless.
barrier is cleared, the O-O distance continues to increase, but
Alternatively, the O2 addition can lead to the formation of
the dioxiranyl radical 8. The latter lies 31.6 kcal/mol lower in the O atom eventually returns to the C6H5O plane and the IRC
energy than the C6H5 + O2 reactants at the G2M level. At path descends to the Cs-symmetric (planar) van der Waals
B3LYP/6-311+G**//B3LYP/6-31G*, the relative energy of 8 complex 2. Further increase of the O-O distance leads to
was earlier calculated to be -19.9 kcal/mol,12 so the difference decomposition of 2 to the phenoxy radical + O. Transition-
between the DFT and the most accurate G2M values exceeds state TS1-2 resides 10.0 kcal/mol below the initial C6H5 + O2
10 kcal/mol. The dioxiranyl radical has a C2V-symmetric reactants and is 36.3 and 0.4 kcal/mol higher in energy than
structure, with the planes containing the six- and three-member intermediates 1 and 2, respectively, but 0.9 kcal/mol lower in
rings perpendicular to each other, and the 2B1 electronic state. energy than the products C6H5O + O. Experimental heat of
With the same C2V symmetry point group, the electronic state formation for the phenylperoxy radical is not available, but we
of the separated C6H5 and O2 reactants is 2B2, which makes the can compare with experiment the calculated heat of the C6H5
reaction forbidden within C2V symmetry. However, if the + O2 f C6H5O + O reaction. The agreement is quite close
symmetry breaks, the oxygen molecule may, in principle, attach both at the G2M and B3LYP/6-311+G**//B3LYP/6-31G* level,
to C6H5 forming 8 without any barrier. If O2 approaches the -9.1 and -6.312 kcal/mol, respectively, versus -8.2 ( 2.0 in
phenyl radical asymmetrically and out-of-plane, some trajec- experiment.22
tories may, in principle, bypass the transition state separating Earlier results by Fadden et al.12 for TS1-2 (TS1-3 in their
intermediates 1 and 8 and go directly to 8. When we tried to study) appear to be not reliable. The transition state for the O
locate an asymmetric transition state connecting the reactants atom loss from 1 was calculated to be 52.4 and 10.1 kcal/mol
with 8, the search did not result in any saddle-point structure higher in energy than the phenylperoxy radical and phenoxy +
but led to the C6H5 + O2 dissociation. However, the possibility O products, respectively. Thus, the error in the forward barrier
of the direct barrierless formation of dioxiranyl from the height was about 16 kcal/mol as compared to the present G2M
reactants is only hypothetical at this stage; ab initio molecular result. The origin of such deviation is not in the use of the
dynamics (MD) simulations have to be carried to confirm that B3LYP method, because the present B3LYP/6-311++G**
such trajectories from C6H5 + O2 to 8 actually exist and to calculations give the barrier at TS1-2 as 33.7 kcal/mol,
evaluate their importance. reasonably close to the G2M value. Instead, Fadden et al.
6118 J. Phys. Chem. A, Vol. 109, No. 27, 2005 Tokmakov et al.

Figure 3. Optimized geometric structures of the van der Waals [C6H5O‚‚‚O] complex (2) and transition-state TS1-2 separating this complex from
the phenylperoxy radical C6H5OO (1). Selected geometric parameters are shown (bond lengths in Å, bond angles and dihedral angles in degrees)
as calculated at the B3LYP/6-311++G** and B3LYP/6-31G* (in parentheses) levels of theory.

apparently have not located the correct geometry for the O-loss mol higher in energy than C6H5O. The second reaction step, 4
transition state; the structure reported in their work is rather f 5, exhibits the highest barrier of 53.8 kcal/mol with respect
different from TS1-2 found here, as it is nearly planar and the to the initial reactant C6H5O and is expected to be rate-
dissociating oxygen is positioned closer to one of the CH groups determining. The present G2M(MP2) relative energies of
than to the second O atom (see Figure 3). intermediates and transition states closely agree with the
It is worth noting again the similarity between the C2H3OO earlier G2M(rcc,MP2*) values.26 The only notable quantitative
(vinylperoxy)21 and C6H5OO (phenylperoxy) systems. On the change is a slight increase of the rate-limiting barrier at TS3-4
dissociation pathway of C2H3OO to C2H3O + O, the transition from 52.2 kcal/mol at G2M(rcc,MP2*) to 53.8 kcal/mol at
state lies 38.6 kcal/mol above the initial intermediate and, after G2M(MP2). In our previous study,26 we have also found that
the barrier is cleared, the C2H3O‚O van der Waals complex is RCCSD(T) and CASPT2 relative energies27 with the same
formed, which is stabilized by 5.7 and 4.0 kcal/mol with respect 6-31G** basis are similar in this system indicating that the
to the transition state and C2H3O + O, respectively. A minor coupled-cluster method, which is in the base of G2M calcula-
quantitative difference between the two systems is found in the tions, properly accounts for nondynamical correlation effects.
relative energies of the O-O bond scission transition states with Oxygen Insertion into the Benzene Ring. Instead of losing
respect to products; the transition state for the vinylperoxy case the terminal O atom, the phenylperoxy radical 1 can undergo
is 1.7 kcal/mol higher in energy than C2H3O + O, whereas for various rearrangements, which can eventually lead to different
phenylperoxy the corresponding transition state is 0.9 kcal/mol reaction products. We start from considering the reaction
lower in energy than C6H5O + O. In addition, the C2H3O‚O mechanisms involving insertion of an oxygen atom into the
complex is more strongly bound (by 4.0 kcal/mol) than C6H5O‚ aromatic ring. First, 1 can isomerize to the dioxiranyl radical 8
O 2 (only by 1.3 kcal/mol). through a closure of the three-member COO ring, overcoming
Now, we briefly recap the most favorable decomposition a barrier of 24.3 kcal/ mol at TS1-8. The barrier height
mechanism of the phenoxy radical 3, C6H5O f TS3-4 f 4 f calculated for this process is again similar to the COO ring-
TS4-5 f 5 f TS5-7 f C5H5 (7) + CO, which was studied closure barrier in the C2H3OO system, 25.0 kcal/mol at the same
in detail earlier by us and by other groups.23-28 The first step G2M level of theory.21 Next, one of the oxygens inserts into
involves a formation of a fused bicyclic cyclopropanone the ring to produce 2-oxepinyloxy radical (10), which contains
intermediate 4 (42.6 kcal/mol above 3) via a 49.7 kcal/mol six carbon atoms and one oxygen atom forming a seven-member
barrier at the transition-state TS3-4. This is followed by ring, with the second O attached to one of the two C atoms
breaking a CC bond of the three-member ring with a barrier of adjacent to the ring oxygen. This rearrangement is rather
53.8 kcal/mol relative to 3 (TS4-5), which leads to intermediate complicated and deserves a detailed consideration. Fadden et
5 residing 31.2 kcal/mol above 3. Subsequently, 5 loses carbon al.12 have found an intermediate structure 9 (see Figure 4) lying
monoxide to produce the cyclopentadienyl radical 7. The barrier between 8 and 10, but the calculated energy of TS9-10
for the last reaction step is 36.5 kcal/mol with respect to the connecting 9 and 10 was lower than that of 9 even without ZPE
phenoxy radical, and the C5H5 + CO products lie 18.1 kcal/ corrections at the B3LYP/6-31G* level, at which these stationary
Reaction of Phenyl Radical with Molecular Oxygen J. Phys. Chem. A, Vol. 109, No. 27, 2005 6119

Figure 4. Molecular structures and energetics of the open-shell radical 9 in different doublet electronic states optimized by the B3LYP/6-311++G**
method with symmetry constraints. Schematic IRC pathways illustrate connections from the 2B1 and 2B2 states of radical 9 to intermediate 10. All
energies are in kcal/mol relative to C6H5 + O2. VRI denotes a valley-ridge inflection point.

structures were optimized. This means that TS9-10 actually and eventually inserts into the adjacent C-C bond on the left,
cannot connect 9 and 10 and should correspond to another just forming the structure 10′ equivalent to 10. Interestingly,
rearrangement. IRC calculations for TS9-10 performed at the TS10-10′ has Cs symmetry, but the mirror plane is perpen-
B3LYP/6-31G* level showed that TS9-10 connects intermedi- dicular to the ring and contains the CO2 group.
ate 10 with itself (more precisely, with its mirror image 10′ Intermediate 9 has a molecular structure similar to that of
with respect to the plane perpendicular to the molecular plane) the dioxiranyl radical 8, but with the O-O bond cleaved. From
and should be denoted as TS10-10′. During the rearrangement the electronic structure point of view, 9 can be characterized as
involving this TS10-10′, the ring O atom, say, on the right, a triradical, since it has three low-spin coupled (2R + 1β)
leaves the molecular plane, rotates about the exocyclic CO bond, unpaired electrons. Two of those are centered on two oxygen
6120 J. Phys. Chem. A, Vol. 109, No. 27, 2005 Tokmakov et al.

atoms and the third electron belongs to the π-system of the C6 example, the exocyclic O1 atom in the reactant form becomes
ring. Like 8, 9 has C2V symmetry, but because of the presence endocyclic in the product form, while the endocyclic O2 atom
of three nearly degenerate singly occupied orbitals, 9 may have moves in the opposite direction to the exocyclic position.
several low-lying electronic states, different in symmetry but We have also optimized two other possible electronic states
close in energies.29 of 9, 2A1 and 2A2. The optimized structures for these states
We need to determine first what electronic state of 9 lies on appeared to be true local minima without imaginary frequencies,
the reaction path from 8 to 10. The electronic state of but they, respectively, lie 15.0 and 18.5 kcal/mol above 9(2B2)
intermediate 8 is 2B1. A search of a transition state for the O-O at the B3LYP/6-31++G** level. The 9(2A1) structure was
bond cleavage in 8 gives TS8-9, which is also C2V-symmetric actually reported by Fadden et al.12 We can conclude here that
with the 2B1 electronic state. IRC calculations for TS8-9 in the 2B2, 2A′, 2A1, and 2A2 electronic states of 9 are not involved
the reverse direction confirm the connection of this transition in the 8 f 10 rearrangement and that only the 2B1 state
state with intermediate 8, and in the forward direction these represents a stationary point (though not a local minimum or a
calculations naturally give a stationary point 9 in the same 2B1 critical transition state) on the pathway of oxygen insertion into
state (Figure 4). However, the vibrational frequency analysis the benzene ring.
of 9(2B1) shows that it has one imaginary frequency of 181i Now, when we have established the mechanism for the
cm-1. As seen in Figure 4, a motion along the eigenvector oxygen insertion into the aromatic ring, we can look more
corresponding to this imaginary frequency breaks C2V symmetry closely at the energetics of this process. The barrier calculated
and maintains only Cs symmetry, with the mirror plane for the 8 f 10 process is 12.7 kcal/mol, as the corresponding
perpendicular to the ring and containing the CO2 fragment and transition-state TS8-9 resides 18.9 kcal/mol below the initial
the CH group located at the opposite side of the ring. IRC reactants at the G2M level. This barrier is 3.1 kcal/mol higher
calculations starting from 9(2B1) both in forward and reverse than the barrier at TS1-8 for the reverse 8 f 1 isomerization
directions lead to TS10-10′ (Cs, 2A′), which in turn has one (opening of the three-member COO ring). The relative energies
imaginary frequency with the eigenvector directed out of the of TS1-8 and TS8-9 are critical for the reaction mechanism,
symmetry plane. since the insertion of the oxygen atom into the ring may lead
As we have already discussed above, IRC calculations for to several various reaction products, as will be described below,
TS10-10′ converge to the equivalent forms of intermediate 10 whereas the reverse 8 f 1 rearrangement may be followed by
in both directions; the forward and reverse local minima differ the oxygen loss resulting in the C6H5O + O and, eventually,
only by the left or right positions of the ring oxygen with respect the C5H5 + CO + O products. We can compare the present
to the exocyclic CdO bond. The potential energy profile shown results for the C6H5/O2 system with the corresponding barrier
in Figure 4 illustrates that 9(2B1) represents a transition state heights for C2H3/O2.21 For the latter, the barriers for the three-
connecting four equivalent structures 10, which could be member COO ring opening and for the insertion of the oxygen
distinguished from one another only if two O atoms and the atom into the CdC bond of the vinyl fragment (passing through
left and right positions of one of them in the ring were a metastable intermediate with O bridging the C-C bond) were
distinguishable. We can also see that transition-state TS8-9 earlier calculated at the G2M level to be 16.9 and 24.0 kcal/
connects local minima 8 and 10, while the detailed reaction mol as compared to 9.6 and 12.7 kcal/mol, respectively, for
pathway is the following: 8 f (up in energy) f TS8-9 f C6H5/O2. We can see that in the phenyl system both barriers
(down in energy) f 9(2B1) f (down in energy) f TS10-10′ decrease, their relative order remains the same, and the
f (down in energy) f 10. Despite an apparent complexity of difference in the barrier heights decreases from 7.1 kcal/mol
this reaction path, the only fact, which matters for the kinetics for C2H3/O2 to 3.1 kcal/mol for the present system. This may
of this rearrangement, is that the transition-state TS8-9 connects have some implications for the temperature-dependent product
intermediate 8 with intermediate 10. This conclusion is con- branching ratios for the phenyl + O2 reaction. A detailed
firmed by calculations of vibrational frequencies for points along investigation of this issue requires multichannel RRKM calcula-
the IRC for TS8-9, which indicate that there is a valley-ridge tions of the reaction rate constant, which will be the subject of
inflection point (VRI) less than 5 pm/amu0.5 away from TS8-9 our future work.
in the forward direction. The rest of the IRC calculation in the In a recent publication,30 Carpenter has questioned the
forward direction follows a ridge all the way to 9(2B1) while accuracy of the single-reference-based G2M approach for the
the valleys near this ridge go directly to different forms of 10. relative barrier heights in the vinyl + O2 system. Using the
The 2B1 state is not the lowest electronic state of 9. An multireference CASPT2 method with the (23,15) active space
optimization of the 2B2 electronic state gives a structure 9(2B2) and pVTZ basis set, he found the barrier for the COO ring
with an energy 4.8 kcal/mol lower (at the B3LYP/6-31++G** opening and for the O insertion into the CdC bond in the C2H3/
level) than that of 9(2B1). However, 9(2B2) has two imaginary O2 system to be 11.9 and 12.5 kcal/mol, respectively, so that
frequencies at the B3LYP/6-31G* level of theory and one the difference between them decreases from 7.1 to merely 0.6
imaginary frequency at B3LYP/6-311++G**. Lowering the kcal/mol when a seemingly more accurate multireference
symmetry constraints and using B3LYP/6-311++G** IRC method is employed. Two aspects of these calculations cause
calculations (see Figure 4), we were able to follow a contin- some concern. First, although the (23,15) active space is
uous descent from 9 (C2V, 2B2) to another stationary point, nominally large, it actually includes only three unoccupied
TS10(O1exo)-10(O2exo) (Cs, 2A′). TS10(O1exo)-10(O2exo) again molecular orbitals (MOs) and may not be flexible enough.
is not a local minimum but a transition state with one imaginary Second, CAPST2 is a perturbation theory method and it is, in
frequency. This structure has the symmetry plane passing general, inferior with respect to the more expensive MRCI
through the ring and reflecting the two oxygen atoms, and the methodology.17,31 Therefore, we recently carried out MRCI
imaginary frequency vibration moves the O atoms in opposite calculations for the two transition states in the C2H3/O2 system.
directions destroying Cs symmetry. IRC calculations for A detailed account of this study will be published elsewhere;32
TS10(O1exo)-10(O2exo) show that this transition state connects here, we only briefly mention the most important result. We
two equivalent forms of 10 with interchanged O-atoms, for used a (9,9) active space in our MRCI calculations, which
Reaction of Phenyl Radical with Molecular Oxygen J. Phys. Chem. A, Vol. 109, No. 27, 2005 6121

21 occurs by the rotation of the C(H)O group containing the

ring oxygen. Once this rotation takes place via TS10-21, the
ring C-O bond is broken and an open-chain intermediate 21 is
produced. The barrier at TS10-21 is calculated to be 26.7 kcal/
mol relative to 10 and the transition state is located 69.7 kcal/
mol below the initial reactants. Isomers 10 and 21 lie 96.4 and
76.7 kcal/mol lower in energy than C6H5 + O2, respectively.
Next, the (H)CCO group in 21, which contains the oxygen atom
formerly being the out-of-ring Oexo in 10, can be rotated leading
to another open-chain isomer 22. The barrier on this pathway
is only 7.9 kcal/mol and 22 is 2.1 kcal/mol more favorable than
21. The next step is again a rotation of the C(H)O group leading
to isomer 23 via a low barrier of 5.8 kcal/mol at TS22-23. 23
has a planar structure with the 2A′′ electronic state and is the
most stable among the three open-chain intermediates, 5.0 and
2.9 kcal/mol lower in energy than 21 and 22, respectively (81.7
kcal/mol below the initial reactants). This stabilization owes to
the hydrogen H...O bond between two opposite ends of the chain
with the H-O distance of 1.904 Å (see Figure 5). Alternatively,
23 can be formed directly from 10 by the ring opening triggered
by rotation of the (H)CCOexo fragment. In this case, the barrier
at TS10-23 is 26.4 kcal/mol, 0.3 kcal/mol lower than the barrier
at TS10-21.
As seen in Figure 6, the chain isomer 23 can undergo a six-
member ring closure via TS23-17 to form the intermediate 17.
At the transition state, the (H)CCO fragment rotates and its C1
Figure 5. The ring-opening mechanism of the intermediate 10. atom is drawn closer to the Oring atom with the C-O distance
of 1.876 Å. The C-O bond formation is completed after TS23-
17 leading to the six-member ring structure 17 with the COexo
consists of all orbitals having electron populations between 1.98
group connected to the ring. The barrier at TS23-17 is
and 0.02 in the CASSCF wave function. The active space in
calculated to be 29.3 kcal/mol relative to 23, but the transition
the initial CASSCF calculations was (9,12), which includes
state is 52.4 kcal/mol lower in energy than the reactants. 17
seven unoccupied MOs and is therefore much wider (in terms
easily decomposes to C5H5O (pyranyl) + CO (18) via TS17-
of the number of configuration state functions, CSFs) than the
18 by cleaving the out-of-ring C-C bond. The transition state
(23,15) active space used by Carpenter. At the MRCI(9,9)/pVTZ
has a rather early character with the breaking C-C bond
level with Davidson corrections for quadruple excitations, the
elongated from 1.593 in 17 to 1.842 Å in TS17-18, and the
barriers for the COO ring opening and for the O insertion into
barrier is only 2.7 kcal/mol relative to 17. The 17 f C5H5O +
the CdC bond are calculated to be 14.5 and 16.9 kcal/mol,
CO dissociation is exothermic by 17.5 kcal/mol and the final
respectively. The barrier heights for the O insertion calculated
products, pyranyl and carbon monoxide, lie 90.7 kcal/mol below
by the MRCI and CCSD(T) methods with the same pVTZ basis
the C6H5 + O2 reactants. The overall lowest energy pathway
set differ only by ∼1 kcal/mol, whereas the value obtained at
to these products is the following: C6H5 + O2 f 1 f 8 f 10
the CASPT2(9,9)/pVTZ level underestimates the most reliable
f 23 f 17 f C5H5O + CO. After intermediates 1 or 8 are
MRCI result by 6.4 kcal/mol. Unfortunately, meaningful multi-
formed at the initial reaction step, the rate-determining step for
reference calculations for the C6H5/O2 system with a proper
the production of pyranyl + CO is the 8 f 10 rearrangement
active space are still beyond modern computational facilities
(oxygen insertion into the aromatic ring) with TS8-10 residing
and for now we have to rely upon the G2M results keeping in
27.4 kcal/mol above 1 but 18.9 kcal/mol below the reactants.
mind their possible inaccuracies illustrated for C2H3/O2. Nev-
ertheless, the multireference effects for TS1-8 and TS8-9 in Several other, somewhat less favorable, pathways leading
the C6H5/O2 system are expected to be smaller than for the from 10 to 17 and therefore to the C5H5O + CO products are
corresponding transition states in C2H3/O2 because the T1 also possible. First, 10 can directly rearrange to the precursor
diagnostic values in CCSD calculations (mean root square of for CO loss via TS10-17 (see Figure 6). During this process,
the singles amplitudes)31 are 0.017 and 0.023 for the former the C2-Oring bond in the seven-member ring breaks, while the
system, notably lower than 0.053 and 0.041 for the latter system, new C1-Oring bond is formed to produce a six-member ring
respectively. structure. The 10 f 17 isomerization is 23.2 kcal/mol endo-
Aromatic Ring Opening/Closure and Formation of the thermic and the transition state exhibits a late character, with
C5H5O (Pyranyl) + CO Products. The seven-member ring the C2-Oring and C1-Oring distances for the breaking and
2-oxepinyloxy radical 10 can undergo ring-opening rearrange- forming bonds of 2.441 and 1.937 Å, respectively. The barrier
ments followed by various ring closures eventually leading to at TS10-17 is 47.5 kcal/mol and the transition state lies 3.5
a six-member ring intermediate 17 with one oxygen atom within kcal/mol higher in energy than TS23-17, which is the highest
the ring and an out-of-ring CO group. 17 is a precursor of the in energy transition state for the 10 f 23 f 17 sequence, thus
C5H5O (pyranyl) + CO products. The ring-opening processes making the direct 10 f 17 isomerization less favorable than
connecting together intermediates 10, 21, 22, and 23 are the two-step process.
illustrated in Figure 5. All of them can be described in terms of Alternatively, the open-chain intermediate 21 can undergo
rotations of the C(H)Oring and (H)CCOexo fragments around the ring closure with the formation of a new C-C bond leaving
adjacent C-C bonds. For instance, the isomerization of 10 to both oxygen atoms in out-of-ring positions and restoring the
6122 J. Phys. Chem. A, Vol. 109, No. 27, 2005 Tokmakov et al.

Figure 6. Various ring-closure pathways of the open-chain intermediates.

C6 aromatic ring (Figure 6). This process occurs via TS20-21 CHART 1
and leads to intermediate 20, which can be referred to as
o-C6H4O(O)(H) indicating that the two out-of-ring oxygens are
located in ortho-position with respect to each other and that
there is a C(H)(O) group in one of the ring apexes. Then, the
oxygen atom of this group can migrate to occupy a bridging
position above the C-C bond in the ring in meta-position
relative to the other terminal O atom, producing intermediate
25, m-C6H5O(O)br. At the G2M level, 20 resides 65.1 kcal/mol
below the initial reactants and 3.0 and 3.3 kcal/mol lower in
energy than transition-states TS20-21 and TS20-25, separating
20 from the structures 21 and 25, respectively. The low barrier
heights indicate that 20 is likely to be a short-living intermediate.
Nevertheless, it is a pivotal intermediate involved in several
reaction mechanisms to be discussed in this and subsequent
sections. For instance, two pathways lead from 20 to the CO-
loss precursor 17 and therefore to the pyranyl + CO products. effective electron delocalization between its resonance structures
In the first mechanism, the oxygen atom of the C(H)(O) group (see Chart 1). Subsequently, 26 can rearrange to a bicyclic
in 20 migrates to a position above the carbon ring and forms a intermediate 27, in which one of the C-C bonds in the C5O
new C-O bond with the carbon on the opposite side of the cycle is bridged by the CO group. This process occurs by the
ring, producing intermediate 33. The latter can be characterized formation of a new C-C bond between two carbons in 26, and
as a bicyclic structure; in addition to the C6 ring, it also includes the barrier is 30.7 kcal/mol. Finally, the CO group in 27 migrates
a four-member C3O ring in a different plane. The barrier at from the bridging to the terminal position breaking one of the
TS20-33 is 19.8 kcal/mol relative to 20 and the bicyclic C-C bonds it is attached to in the C5O ring, and structure 17
intermediate is 68.2 kcal/mol lower in energy than the initial is produced over a barrier of 15.0 kcal/mol at TS27-17.
reactants. At the next step, one of the C-C bonds in the C6 When we compare four different mechanisms leading from
ring adjacent to the CdO group breaks and the bicyclic structure 10 to the pyranyl + carbon monoxide products via the precursor
turns into the C5O six-member ring with an out-of-ring CO 17, 10 f 23 f 17, 10 f 17, 10 f 21 f 20 f 33 f 17, and
group, that is, intermediate 17. The barrier between 33 and 17 10 f 21 f 20 f 26 f 25 f 27 f 17, we find that the pathway
is calculated to be 15.5 kcal/mol relative to the former. via 23 is the most favorable energetically as the highest in energy
In the second mechanism, 20 first isomerizes to 25 and then transition state on this path, TS23-17, lies 52.4 kcal/mol below
the latter rearranges to 3-oxepinyloxy radical 26 by β-scission the initial reactants. The direct isomerization of 10 to 17 has
of the CC bond of the epoxy ring. The corresponding barrier the transition state 48.8 kcal/mol lower in energy than C6H5 +
(at TS25-26) is 17.5 kcal/mol with respect to 25. Both isomers O2, while the pathway via 33 and those via 26 and 27 exhibit
26 and 10 have the same oxepinyl ring unit; they differ only in the highest in energy transition states 45.3 (TS20-33) and 38.4
the relative position of the exo- and endocyclyc O atoms, ortho (TS27-17) kcal/mol below the reactants, respectively.
in 10 versus meta in 26. Nevertheless, the energies of the two Migration of Oxygen Atom around the Aromatic Ring
isomers are rather different; 26 lies 74.5 kcal/mol below the and Formation of Benzoquinone Products. As we already
reactants but 21.9 kcal/mol above 10, as the latter allows a more saw in the previous section, the o-C6H4O(O)(H) intermediate
Reaction of Phenyl Radical with Molecular Oxygen J. Phys. Chem. A, Vol. 109, No. 27, 2005 6123

The m-C6H4O(O)(H) structure 34 may also exist as a

metastable intermediate, 19.4 kcal/mol below the initial reactants
but 50-60 kcal/mol higher in energy than the m- and p-bridge
isomers 24 and 25 and the p-C6H4O(O)(H) structure 28. A
careful search for oxygen migration transition states in the
vicinity of 34 shows that it can be produced only from 24 and
is separated from the latter by a low barrier of only 1.6 kcal/
mol (TS24-34) at the B3LYP/6-311++G** level. At the G2M
level, the energy of TS24-34, -27.8 kcal/mol relative to C6H5
+ O2, is lower than that of 34 indicating that at this level of
theory this intermediate is not likely to be a local minimum.
From 34, the system can progress by a 1,2-H shift from the
carbon atom of the C(O)(H) group to the neighboring oxygen
leading to the structure 35, which consists of the C6 ring with
a terminal O atom and an OH group. At the G2M level, the H
migration barrier is calculated to be 9.0 kcal/mol relative to
34. If 34 is not a local minimum, 24 rearranges to 35 directly
overcoming the barrier of 60.4 kcal/mol at TS34-35. The
Figure 7. The mechanism of the O-atom migration around the C6 ring. resulting isomer 35 lies 109.0 kcal/mol lower in energy than
C6H5 + O2. 35 is an OH-substituted analogue of the phenoxy
20 can be produced from 10 via the open-chain isomer 21. radical and can, in principle, decompose to C5H4OH (OH-
Fadden et al.12 also found a transition-state TS10-20 at the substituted cyclopentadienyl) + CO by the mechanism described
B3LYP/6-31G* level, which connects 10 and 20 directly. At above for C6H5O or be a precursor for the OH group loss to
the B3LYP/6-311+G**//B3LYP/6-31G* level of theory, TS10- give C6H4O + OH. However, the latter channel is highly
20 lies 9.4 kcal/mol above TS20-21. Although we were able endothermic and therefore unlikely, because the C6H4O (38) +
to reproduce the optimized geometry of TS10-20 at B3LYP/ OH products reside 103.9 kcal/mol above 35 (5.1 kcal/mol
6-31G*, at the higher B3LYP/6-311++G** level this transition below the initial reactants). The pathway to 35 goes through
state does not survive as its optimization converges to TS20- 25 and 24 and therefore via TS25-24 (only 29.2 kcal/mol below
21, indicating that the energetically unfavorable direct pathway
the reactants) and TS34-35 (-10.4 kcal/mol) or TS24-36
from 10 to 20 disappears and this rearrangement can occur only
(-22.2 kcal/mol) making the formation of 35 in this reaction
by the two-step mechanism via 21.
improbable because many other reaction pathways (for example,
Once the structure 20 is formed, the oxygen atom can
those leading to 17 and pyranyl + CO products) have critical
continue its migration around the ring. The mechanism of this
transition states significantly lower in energy. Therefore, we
migration is illustrated in Figure 7, where we show two
do not consider the decomposition mechanism of 35 in detail
equivalent directions for the oxygen motion, clockwise and
here. An alternative mechanism to produce 35 proceeds from
anticlockwise. The meta-bridge isomer 25, m-C6H5O(O)br, needs
24 via intermediate 36 and involves a 1,2-H shift to form a
to clear a barrier of 50.5 kcal/mol to rearrange to the para-bridge
CH2 group (accompanied with O migration from the para-bridge
structure p-C6H5O(O)br 24 via TS25-24 lying 29.2 kcal/mol
to meta-position) followed by a 1,3-H migration from the CH2
below the initial reactants. Next, the migrating oxygen atom
group to one of the terminal oxygens. The barriers for these
can reach the most remote para-position with respect to the CdO
processes are 48.6 and 22.5 kcal/mol relative to 24. Structure
group, thus forming a structure p-C6H4O(O)(H) 28 after
overcoming a 10.3 kcal/mol barrier at TS24-28. Both 24 and 36 resides in a deep potential well, 108.1 kcal/mol below C6H5
28 have similar energies and reside ∼71 kcal/mol below the + O2, and is only 0.9 kcal/mol less favorable than the isomer
initial reactants but about 9 kcal/mol higher in energy than the 35. Structures 24 and 28 can undergo some other isomerizations
meta-bridge isomer 25. Additional pathways also exist, which not shown in Figure 1, including, for example, the 1,2-H shift
lead to 20, 25, and 28 directly from the initial intermediate 1 in 28 leading to a para analogue of the OH-substituted phenoxy
bypassing the seven-member ring structure 10, but these radical 35 and followed by decomposition of the latter through
pathways are much less favorable energetically. For instance, the CO, H, or OH eliminations or insertion of the bridging O
the terminal O atom in the COO group can form a new C-O into the C-C bond to produce a para structure similar to the
bond with the adjacent carbon in the ring producing a bicyclic seven-member ring isomers 10 (ortho) and 26 (meta). However,
(C6/C2O2) structure 19. The barrier for this rearrangement is since the formation of 24 and 28 in this reaction is rather
calculated to be 41.3 kcal/mol relative to 1 but the corresponding unlikely because of the high barrier at TS25-24, we do not
transition-state TS1-19 is 17.0 and 14.9 kcal/mol, respectively, pursue these mechanisms further.
higher in energy than TS1-8 and TS8-9, the critical transition The intermediates o-C6H4O(O)(H) 20 and p-C6H4O(O)(H)
states on the pathway to the structure 10 and beyond. 19 is a 28 can serve as precursors for the H atom elimination to yield
metastable intermediate residing only 8.3 kcal/mol below C6H5 o- and p-benzoquinones, respectively. For 20, the H loss appears
+ O2, and it is separated from 20 by a very low barrier of 1.6 to be stepwise; the H atom first migrates to make a CH2 group
kcal/mol for the O-O bond cleavage in the four-member C2O2 in intermediate 37 and then is eliminated from the CH2 group.
cycle of 19. Alternatively, the terminal oxygen in 1 can migrate The transition states for the two steps have similar energies and
over the area above the aromatic ring leading directly to the lie about 52 kcal/mol below the initial reactants. The structure
meta-bridge isomer 25 or even to the p-C6H4O(O)(H) structure 37 is rather stable, 98.5 kcal/mol below C6H5 + O2, and the
28. However, these processes are highly unfavorable and can final products, o-C6H4O2 + H, are 53.8 kcal/mol exothermic
be neglected, because the barriers at TS1-25 and TS1-28 are with respect to the reactants. Alternatively, the H atom of the
computed to be 104.3 (58.0) and 88.5 (42.2) kcal/mol, respec- C(H)(O) group in 20 can undergo a 1,2(C,O)-H shift via a barrier
tively, relative to 1 (C6H5 + O2). of 18.1 kcal/mol relative to 20 to form structure 39, an analogue
6124 J. Phys. Chem. A, Vol. 109, No. 27, 2005 Tokmakov et al.

of 35, an ortho-OH-substituted phenoxy radical. 39 is the most adjacent CH group in the ring. At the next step, the connecting
stable structure of all C6H5O2 isomers found in this study, 117.7 C-O bond is broken and the C5H5 + CO2 products are formed.
kcal/mol lower in energy than the reactants. Then, hydrogen The barriers for this two-step decomposition of 11 are higher
elimination from the OH group via TS39-14 leads to the same than that for the pathway involving 12, as the corresponding
o-C6H4O2 + H products. The forward and reverse barriers for transition-states TS11-13 and TS13-7 lie 65.3 and 54.4 kcal/
the H loss/addition are 67.7 and 3.8 kcal/mol relative to 39 and mol lower in energy than C6H5 + O2, respectively. Isomer 13
o-C6H4O2 + H, respectively. For the para-intermediate 28, the resides in a potential well separated from 11 and C5H5 + CO2
H elimination process is direct and proceeds via TS28-16 over by nonnegligible barriers of 7.2 and 18.1 kcal/mol, respectively.
a 17.1 kcal/mol barrier. The transition state and the products, Finally, there exists a third pathway, which leads from the
p-C6H4O2 + H, lie 53.6 and 61.6 kcal/mol lower in energy than dioxiranyl radical 8 to the cyclopentadienyl + CO2 products.
the C6H5 + O2 reactants. Although p-benzoquinone is thermo- This channel proceeds by fusion of the six-member C6 ring in
dynamically more stable than o-C6H4O2 (by 7.8 kcal/mol at the 8 into five-member and three-member cycles in intermediate
G2M level), the former is not likely to be produced in the C6H5 15, followed by elimination of the CO2 group. However, the
+ O2 reaction because of the high barrier on the pathway leading barriers on this pathway are high, 47.3 (15.7) kcal/mol at TS8-
to 28 (at TS25-24). On the other hand, the production of 15 and 58.9 (27.3) kcal/mol at TS15-7 as counted from 8 (C6H5
o-benzoquinone is probably possible because the relative energy + O2), and this reaction channel is not expected to be
of the critical transition state for this channel, -51.9 kcal/mol competitive. C5H5 + CO2 are the most exothermic products as
(TS14-37), is comparable with the energy of the critical TS they lie 114.8 kcal/mol lower in energy than the initial reactants.
on the pathway leading to pyranyl + CO, -52.4 kcal/mol The energetically preferable pathway to these products is 10 f
(TS23-17). H eliminations from the C(H)(O) group in 34, the 11 f 12 f C5H5 + CO2 with the highest in energy transition-
OH group in 35, and the CH2 group in 36 would lead to state TS10-11 residing 61.7 kcal/mol below the reactants. The
m-benzoquinone; however, such an isomer of C6H4O2 does not energy of TS10-11 is about 10 kcal/mol lower than the energies
exist as a stable structure. Therefore, the H losses from 34-36 of the critical transition states on the pathways leading to pyranyl
are unlikely to be favorable energetically and are not considered + CO (TS23-17, -52.4 kcal/mol) and to o-benzoquinone +
here. H (TS14-37, -51.9 kcal/mol). On the basis of these results,
The C5H5 + CO2 Product Channel. Starting from the we could expect that the branching ratio of the C5H5 + CO2
pivotal intermediate 10, the reaction can proceed also to the reaction products should be higher than those for pyranyl and
C5H5 + CO2 products. First, the seven-member C6O ring can benzoquinone; however, RRKM calculations of multichannel
fuse into a bicyclic structure 11 consisting of a five-member reaction rate constants are required to address this issue
C5 and a four-member C3O rings with a common C-C bond. quantitatively.
11 is almost as stable as 10 and resides 95.0 kcal/mol below Pathways to the C4H3O2 + C2H2 Products. Intermediate
the initial reactants. The barrier located at TS10-11 is 34.7 12 (although it is established to be only a transient structure)
kcal/mol with respect to 10, but the transition state lies as deep can not only lose the CO2 group but can also rearrange to
as 61.7 kcal/mol below C6H5 + O2. Two different reaction another bicyclic structure 32 through the formation of a new
channels lead from 11 to the cyclopentadienyl radical + carbon O-C bond with the carbon atom in the ring located in the meta
dioxide products. In the first mechanism, initially the C-O bond position with respect to the out-of-ring C-C bond connecting
in the four-member cycle breaks to form intermediate 12. This C5H5 with CO2. On the contrary to 11, the two five-member
is followed by the cleavage of the C-C bond connecting the rings in 32 are C5 and C4O having two common C-C bonds.
CO2 group with the C5H5 ring resulting in the final products. 32 lies 73.9 kcal/mol below the reactants and the barrier at
However, structure 12, if exists as a local minimum, is a very TS12-32 is 6.1, 8.0, and 29.1 kcal/mol relative to 12, 32, and
unstable intermediate. The B3LYP/6-311++G** geometry 11, respectively. At the subsequent reaction step, one of the
optimization gives 12 as a stationary point on the PES with all C-C bonds in the C5 ring can be broken leading to another
real vibrational frequencies. However, it is only 0.8 and 0.1 intermediate 30, which has a structure of a C4O five-member
kcal/mol more stable than the adjoining transition states TS11- cycle with one out-of-ring oxygen atom and a terminal HCCH
12 and TS12-7, respectively. After ZPE corrections are group both in the ortho position with respect to the ring O. The
included into the energies, 12 is still 1.0 kcal/mol more stable transition state corresponding to this rearrangement, TS32-30,
than TS11-12 but becomes 0.5 kcal/mol higher in energy than resides 46.6 kcal/mol below C6H5 + O2, so the barrier for the
TS12-7. Refinement of the single-point energies at the G2M C5-ring opening in 32 is 27.3 kcal/mol. 30 is a precursor for
level gives the relative energy of 12 (-72.0 kcal/mol) higher the C2H2 elimination; the exocyclic C-C bond can be cleaved
than those of TS11-12 and TS12-7, -77.0 and -76.4 kcal/ overcoming the 22.5 kcal/mol barrier at TS30-31 and resulting
mol, respectively. Therefore, 12 is at most a transient structure in the cyclic C4OH3O (2-oxo-2,3-dihydrofuran-4-yl) + acetylene
on the pathway for the CO2 loss from 11, and this process is products. These products are computed to be 60.5 kcal/mol
most likely to occur in one concerted step in which both the exothermic relative to the reactants, and the highest in energy
C-C and C-O bonds attaching CO2 to the C5H5 group are transition state on the 10 f 11 f 12 f 32 f 30 f C4OH3O
broken together. If 12, which is the highest in energy structure + C2H2 pathway is TS30-31 for the final reaction step, which
on the 11 f C5H5 + CO2 pathway, may be considered as a top lies 43.5 kcal/mol lower in energy than C6H5 + O2. The energy
of the barrier, the C-O bond breaks first, before the barrier, of this transition state is 18.5 kcal/mol higher than that of TS10-
and the C-C bond is cleaved after the barrier is cleared. The 11 (the critical transition state for the 10 f ... f C5H5 + CO2
second channel leading from 11 to the products initiates by the channel) and 8-9 kcal/mol higher than the energies of TS23-
cleavage of the C-C bond in the four-member ring, which can 17 (10 f ... f C5H5O (pyranyl) + CO) and TS37-14 (10 f
also be pictured as a rotation of the CO2 fragment around the ... f o-C6H4O2 (benzoquinone) + H). It is unlikely that such a
O-C bond connecting it to the C5H5 ring. As a result, a rather significant difference in activation enthalpies can be upset by
stable intermediate 13 is produced, which possesses Cs sym- the entropy factor even at high temperatures, so we expect that
metry with the mirror plane containing the CO2 group and the the contribution of the 2-oxo-2,3-dihydrofuran-4-yl + acetylene
Reaction of Phenyl Radical with Molecular Oxygen J. Phys. Chem. A, Vol. 109, No. 27, 2005 6125

Figure 8. Potential energy diagram for the most important channels of the C6H5 + O2 reaction. Relative energies of the reactants, products,
intermediates, and transition states are given in kcal/mol as calculated at the G2M level.

product channel should be very minor. Future calculations of different reaction products, most importantly, cyclopentadienyl
rate constants can assess the role of this channel more radical + carbon dioxide, pyranyl + carbon monoxide, o-
quantitatively. benzoquinone + H, and 2-oxo-2,3-dihydrofuran-4-yl (C4OH3O)
Finally, there is one more channel leading to the intermediate + acetylene. The reaction barriers leading from 10 to this variety
30 and therefore to the C4OH3O + C2H2 products. The C(H)(O) of products are much lower than the reverse barrier from 10 to
group oxygen atom in the p-C6H4O(O)(H) structure 28 can dioxiranyl 8. Therefore, once 10 is produced, it is unlikely to
migrate to occupy a bridging position roughly above the center go back to 8 and 1, and the branching ratio of C6H5O + O
of the C6 ring by forming an extra O-C bond with the carbon against the other products will be mostly controlled by the
on the opposite end of the ring. Such migration produces a critical transition-states TS1-2, TS1-8, and TS8-9 (between
bicyclic intermediate 29, the structure of which can be best 8 and 10). In this regard, the situation here is similar to the
described as two five-member C4O rings with two common vinyl + O2 reaction, for which the branching ratio between the
C-O bonds. One of these rings can be destroyed by cleaving C2H3O + O and other products is mostly governed by the
a single C-C bond and this leads to the structure 30. However, transition states for the COO ring opening and for the O insertion
this process is not expected to be competitive because the into the CdC bond in the dioxiranylmethyl radical.21,30,34,35
transition-states TS28-29, TS29-30, and the intermediate 29 According to the calculated energies, in terms of enthalpies,
involved lie only 19.8, 34.2, and 39.8 kcal/mol below the initial the most favorable product channel for the decomposition of
reactants, and in addition, the structure 28 is not likely to be 10 is C5H5 + CO2, 10 f 11 f 7 + CO2, with the highest in
produced in the first place because of the high barrier at TS25- energy transition-state TS10-11 residing 61.7 kcal/mol below
24. The channel leading to 30 via 11 and 32 is certainly the initial reactants. This pathway is followed by the channels
preferable. leading to pyranyl + CO, 10 f 23 f 17 f C5H5O + CO, and
Summary of the Most Important Reaction Pathways and to o-benzoquinone + H, 10 f 21 f 20 f 37 f o-C6H4O2 +
Conclusions. A simplified potential energy diagram that sum- H, with the critical transition states lying about 52 kcal/mol
marizes the most important channels of the C6H5 + O2 reaction lower in energy than C6H5 + O2. Finally, the channel leading
is illustrated in Figure 8. In this diagram, we have included to 2-oxo-2,3-dihydrofuran-4-yl + acetylene, 10 f 11 f 32 f
only the energetically favorable channels and have omitted ... f C4OH3O + C2H2, has the highest in energy transition-
several metastable intermediates, which are not expected to play state TS30-31 43.5 kcal/mol below the reactants.
any role in the reaction kinetics. The reaction starts with a It is well-known from experiment23-26 and also from theoreti-
barrierless addition of the oxygen molecule to the radical site cal calculations26,27 that the major products of thermal decom-
of C6H5 to produce either phenylperoxy (1) or, possibly, position of the phenoxy radical C6H5O are cyclopentadienyl +
dioxiranyl (8) radicals with exothermicities of 46.3 and 31.6 carbon monoxide. Since C6H5O + O and C5H5 + CO2 are
kcal/mol, respectively. Next, 1 can lose the terminal oxygen expected to be the major primary products of the C6H5 + O2
atom and produce the phenoxy + O products, rearrange to 8, reaction, and C6H5O will then decompose to the secondary
or (less likely) to 25 (via metastable 19 and 20). The fate of 8 products C5H5 + CO, we can conclude here that cyclopenta-
is twofold; it can either isomerize back to the phenylperoxy dienyl radicals should be the most important product of oxidation
radical or rearrange to the 2-oxepinyloxy radical 10, which lies of phenyl radicals by molecular oxygen. Nevertheless, it is
in a deep potential well of 96.4 kcal/mol below the initial important to know the temperature/pressure dependent branching
reactants. Transformations of 10 in turn give rise to many ratios of C6H5O + O versus C5H5 + CO2 because the primary
6126 J. Phys. Chem. A, Vol. 109, No. 27, 2005 Tokmakov et al.

C5H5 product is formed together with an inert CO2 molecule, (13) (a) Becke, A. D. J. Chem. Phys. 1992, 96, 2155. (b) Becke, A. D.
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Taking into account that the C5H5 radical is the ultimate (16) (a) Knowles, P. J.; Hampel, C.; Werner, H. J. J. Chem. Phys. 1993,
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leads to degradation of the six-member aromatic ring to the five- Models; Wiley: New York, 2002.
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of some other products. The C5H5 radicals can again serve as R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, R. E.; Kudin, K.
precursors for the formation of benzene (for instance, via the N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi,
C5H5 + CH3 reaction),36 naphthalene (via the self-reaction),37 R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.;
or even higher PAHs (for example, via the indenyl + C5H5 Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Salvador, P.;
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reaction leading to phenanthrene).38 Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B.
The conclusions concerning the products of the C6H5 + O2 B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin,
reaction and their branching ratios, which we can make here R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara,
A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M.
on the basis of the calculated PES, are only preliminary. To W.; Andres, J. L.; Gonzalez, C.; M. Head-Gordon, M.; Replogle, E. S.;
predict the product branching ratios and their variation with the Pople, J. A. Gaussian 98, revision A.11; Gaussian, Inc.: Pittsburgh, PA,
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to be taken into account and multichannel RRKM calculations (19) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K.
of the reaction rate constants are required. Such calculations N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.;
based on the reaction mechanism outlined in Figure 8 are now Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.;
underway in our groups and they will be reported in future Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.;
Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li,
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Acknowledgment. This work was funded in part by Aca- Pomelli, C.; Ochterski, J.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.;
Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels,
demia Sinica and National Science Council of Taiwan and in A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.;
part by the Chemical Sciences, Geosciences and Biosciences Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.;
Division, Office of Basic Energy Sciences, Office of Sciences Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz,
of the U.S. Department of Energy (Grant No. DE-FG02- P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.;
Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson,
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