DOI: 10.1002/chem.

201902244 Full Paper

& Physical Chemistry

Valence-Shell Electron-Pair Repulsion Theory Revisited: An

Explanation for Core Polarization
Julen Mun#rriz,*[a, b, c] Mjnica Calatayud,[b] and Julia Contreras-Garc&a*[b]

Abstract: Valence-shell electron-pair repulsion (VSEPR) the studied systems follow this trend, providing a framework
theory constitutes one of the pillars of theoretical predictive for predicting electron distribution in the core. We also
chemistry. It was proposed even before the advent of the show that lone pairs behave as “standard ligands” in terms
concept of “spin”, and it is still a very useful tool in chemis- of core polarization. The predictive character of the model
try. In this article we propose an extension of VSEPR theory was tested by proposing the core polarization in different
to understand the core structure and predict core polariza- systems not included in the original set (such as XeF4 and
tion in the main-group elements. We show from first princi- [Fe(CN)6]3@) and checking the hypothesis by means of a pos-
ples (Electron Localization Function analysis) how the inner- teriori calculations. From the experimental point of view, the
and outer-core shells are organized. In particular, electrons extension of VSEPR to the core region has consequences for
in these regions are structured following the shape of the current crystallography research. In particular, it explains the
dual polyhedron of the valence shell (3rd period) or the core polarization revealed by high resolution X-ray experi-
equivalent polyhedron (4th and 5th periods). We interpret ments.
these results in terms of “hard” and “soft” core character. All

Introduction pillar of “chemical intuition” and structural analysis in chemis-

try.[7, 8]
The development of simple models that facilitate a reliable When developing the concepts behind VSEPR, the repulsion
prediction and rationalization of molecular structures and between electron pairs was used to explain the organization of
properties is of great importance in current chemical re- the valence ligands and lone pairs. However, as its name
search.[1, 2] In this regard, a good example of the predictive states, this theory is generally applied to the valence shell, and
character of a simple energy model is the well-known valence- less attention has been paid to the core electrons.[9, 10] Herein
shell electron-pair repulsion (VSEPR) theory. Specifically, it we show that the principles that govern VSEPR theory can be
allows molecular geometries to be predicted in terms of the applied to explain the spatial distribution of all the electrons,
repulsion between electron pairs.[3] This theory has proven to that is, both valence and core electrons. This generalization
work well for main-group-based systems,[4] with only some ex- has obvious epistemological consequences, allowing further
ceptions, especially for complexes bearing a d0 central understanding of the electronic structure of the core regions
atom.[5, 6] Hence, it constitutes, in conjunction with other to be obtained. Moreover, we also highlight its utility in the in-
models, such as Lewis structures and electronegativity, a basic terpretation of new accurate crystallographic data.[11]
Whereas VSEPR theory was postulated relying mainly on
chemical intuition and the empirical observation of a great
number of compositions and stoichiometries, nowadays we
[a] Dr. J. Mun#rriz
Departamento de Qu&mica F&sica, and Instituto de Biocomputacijn y count on tools that are able to reveal electron localization
F&sica de Sistemas Complejos (BIFI), Universidad de Zaragoza from first principles. One such tool is the Electron Localization
Zaragoza 50009 (Spain) Function (ELF).[12] The ELF is a measure of the probability of
[b] Dr. J. Mun#rriz, Dr. M. Calatayud, Dr. J. Contreras-Garc&a finding electron pairs with opposite spins, which makes it an
Laboratoire de Chimie Th8orique (LCT), Sorbonne Universit8
ideal tool for the identification of Lewis entities (the ELF
CNRS, Paris 75005 (France)
E-mail: [email protected] maxima typically appear at bonds and lone pairs).[13] It has
[c] Dr. J. Mun#rriz proven to be very useful in the understanding and prediction
Current address: Department of Chemistry and Biochemistry of chemical properties,[14] as well as in the study of a wide vari-
University of California, Los Angeles, 607 Charles E. Young Drive East ety of reactions, ranging from organic to biochemical and or-
Los Angeles, CA 90095 (USA)
ganometallic, among many others.[15, 16] Within the framework
E-mail: [email protected]
of this contribution, we should highlight the work performed
Supporting information and the ORCID identification number(s) for the
author(s) of this article can be found under: by Gillespie and co-workers, who were able to explain the dis-
https://doi.org/10.1002/chem.201902244. tortions of different metallic compounds from the VSEPR ge-

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ometry by applying the ELF to study the interactions between

the valence shell ligands and the outer-core regions.[9, 17]
This type of analysis holds an inherent interest for the inter-
pretation of new and more accurate spectroscopies. High-
energy[18, 19] and high-pressure[20] processes have led to interest-
ing novel chemical phenomena in which electrons vacate the
core or even leave the atom. This leads to a need to under-
stand the subtle electron structure of the core. As an example,
the inclusion of core deformations in the resolution of X-ray
data is a current field of development in crystallography.[21]
Crystallographic structures are usually resolved by resorting to
a multipolar approximation.[22] In this approach, the cores are
kept frozen, whereas the valence deforms to fit the experimen-
tal structure factors by using multipoles.[23] However, it was re-
cently proposed that for the appropriate resolution of accurate
data, the core regions should also be allowed to deform.[11]
Herein, we further confirm the existence of such deformations
from a theoretical point of view, by reproducing and explain-
ing the core deformations reported for a-silicon.[24]
This paper is organized as follows. First, we introduce the
concept of the dual and equivalent polyhedra, which will allow
us to set the geometrical basis of the model. Then, we analyze Figure 1. Schematic representation of: a) the LOCC and b) the dual poly-
the maxima of the ELF in the core region of a set of VSEPR-ge- hedron of a tetrahedron and an octahedron.
ometry molecules with the central elements belonging to the
representative groups of the periodic table, so as to unravel
the connection between the core organization and the valence the LOCC principle). However, for an octahedral system such as
shell distribution. In particular, we interpret the localization SF6, the ELF localization maxima do not lead to LOCCs (which
patterns that arise in a number of VSPER molecular geometries, would result in an octahedron with the same orientation as
with the central atoms belonging to the 3rd, 4th, and 5th peri- the ligands, as depicted in Figure 1 a). On the contrary, a cubic
ods. Within these, we first focus on the core structure of mo- organization is observed. This leads to a reformulation of the
lecular systems with stoichiometries AX6, AX4, AX5, and AX3 (in principle guiding the outer-core organization. In this contribu-
decreasing order of symmetry). Then, we evaluate the effect tion, we show that in general, core organizations do not re-
that valence-shell distortions have on the core structure. The spond to an electron localization opposed to the ligands, but
consistency of the results has allowed us to propose some in- to a general organization in terms of the overall geometrical
ductive general rules that enable the organization of the core disposition of the ligands and the period to which the central
to be predicted, and these are summarized at the end of the atom belongs. This leads to the appearance of the dual and
paper. Finally, the predictive power of the model is verified by the equivalent polyhedra.
1) explaining the experimentally determined core polarization The dual polyhedron (DP) is the one that results from plac-
of a-silicon[24] and 2) predicting the core polarization of some ing a vertex in the middle of the face of the original polyhedra
test systems that are outside the group we used for elaborat- (see Figure 1 b). This principle allows the shape of the localiza-
ing the model. tion maxima observed in the two previous examples to be ex-
plained, because the dual polyhedron of an octahedron is a
cube (and vice versa), and that of a tetrahedron is another tet-
Results and Discussion
rahedron with an inverted orientation (see Figure 1 b). These
Historically, the organization of the outer core in metals has results anticipate the core structure to be intimately related to
been studied by means of an analysis of the electron density the valence shell, and thus, the pertinent extension of VSEPR
maxima within the quantum theory of atoms-in-molecules theory to the core regions. If this is the case, what happens as
(QTAIM) approach.[25] A principle known as ligand-opposed we go to the inner core? Whereas the previous few studies fo-
charge concentration (LOCC) was put forward. It states that cused on the outer core,[9] the concept of the dual polyhedron
the core localization maxima are located in the opposite direc- has encouraged us to analyze the whole core structure of cen-
tion to the ligands so as to minimize the repulsion between tral atoms belonging to the 3rd, 4th, and 5th periods. As previ-
electron pairs, as exemplified in Figure 1 a for tetrahedral and ously stated, we have paid special attention to the relationship
octahedral geometries.[26] Nonetheless, a mere opposition of between the ligand distribution in the valence shell and the
electron pairs does not always explain the organization of the core structure, and how distortions in the valence shell affect
electron localization maxima predicted by the ELF. For exam- the core organization.
ple, for a tetrahedral system such as SiF4, the core ELF maxima
have the shape of an inverted tetrahedron (in agreement with

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AX6 stoichiometries Namely, the outer core directly polarizes following the valence
shell, that is, the ELF maxima in the core are ligand-oriented,
First, we considered simple octahedral molecules (Oh symme- having the shape of the equivalent polyhedron (EP). As a con-
try). The details of the calculations are presented in the Experi- sequence, octahedra are observed for the first core shell in the
mental Section. In particular, we began by investigating the 4th and 5th row elements, as exemplified in Figure 2 b,c for
AX6(Z) geometries (A = S, P, and Cl, X = H, F, and Cl, and Z repre- AsF6@ and SbF6@ , respectively (see Table S5 in the Supporting
sents the pertinent molecular charge, see Table S5 in the Sup- Information for more examples). Because relativistic effects
porting Information). Note that because the ELF respects the may be important in these systems,[27] we applied the relativis-
symmetry of the system, it only shows one maximum situated tic zeroth-order regular approximation (ZORA) in 5th row calcu-
at the core position for the first core shell (2nd period ele- lations, as explained in the Experimental Section.
ments). Hence, the ELF can only be used to analyze the outer- We believe this finding paves the way to the extension of
core polarization of central atoms having at least two core the chemical hard and soft character to the core regions.[28]
shells, that is, those that belong to the 3rd period onwards. In Atoms belonging to the 3rd period would exhibit a hard core
all the studied cases, the core region reflected the repulsion character, and thus counter-polarize with respect to the elec-
with respect to the valence shell, leading to the corresponding tron pairs in the valence shell (DP). In contrast, the outer core
dual polyhedron: The localization maxima in the core for this of atoms of the 4th row on would exhibit a soft core character.
set of molecules have the shape of a perfect cube (see Fig- Hence, they undergo direct polarization (EP) with respect to
ure 2 a for the case of PF6@). To unravel whether this is a the valence ligands. Note that the inner-core shells are also or-
common trend for the outer core, the central atoms were sub- ganized in terms of the dual and equivalent polyhedra (see the
stituted by those belonging to the 4th and 5th periods. Specifi- whole core structures depicted in Figure 2).
cally, we considered selenium, arsenic, bromine (4th row), tellu-
rium, antimony, and iodine (5th row). To our surprise, for these
systems, a different kind of core polarization was observed. AX4 stoichiometries
The previous results prompted us to extend the analysis to tet-
rahedral molecules (Td symmetry). In particular, the general sto-
ichiometries AX4(Z) with central atoms belonging to the 3rd (A =
Si, Al, and P), 4th (A = Ge, Ga, and As), and 5th (A = Sn, In, Sb)
periods and with X = H, F, and Cl, and the pertinent molecular
charges were considered (see Table S6 in the Supporting Infor-
mation). Interestingly, the same general behavior as for the
AX6 systems was observed. Namely, direct counter-polarization
happened for the 3rd row atoms. The dual polyhedron of the
ligand shell was reproduced in the core, giving an inverted tet-
rahedron, as depicted in Figure 3 a for SiCl4. In contrast, the 4th
and 5th row atoms undergo direct polarization. As a conse-
quence, the equivalent polyhedron was obtained in the core
region, that is, a tetrahedron oriented in the same direction as

Figure 3. Outer and inner core polyhedra for a) SiCl4, b) GeCl4, and c) Ge
Figure 2. Outer and inner core polyhedra for: a) PF6@ , b) AsF6@ , and c) SbF6@ . core of GeCl4. Chloride ligands are depicted in green, and core ELF maxima
Fluoride ligands are depicted in blue, and core ELF maxima in purple. in purple.

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the ligand shell (see Figure 3 b for GeCl4). Again, the same kind ure 4 c). As depicted in Figure 4 c, the expected DP polyhedron
of behavior, that is, organization in terms of the EP and the DP, in AlH3 (and in general AX3 systems) is formed. However, it is
was found in the inner core. As presented in Figure 3 c for ger- accompanied by another two axial localization regions. It
manium (4th row), the outer core has the shape of the EP of should be noted that within the D3h group, the axial and equa-
the valence shell, whereas the inner-core localization maxima torial maxima form two different reducible representations.
form the DP of the outer core (see Figure S1 for additional de- The appearance of these “extra” maxima in addition to the pre-
tails). dicted ones requires further analysis. As expected, from the 4th
row on, the outer core undergoes direct polarization (see Fig-
ure 4 d). Thus, the electron localization maxima have the shape
AX5 stoichiometries of a triangle oriented towards the ligands (EP). The inner-core
Less symmetrical valence-shell geometries were also evaluated. shells are also structured in terms of the DP and EP, as shown
In particular, we considered trigonal-bipyramidal and triangular in Figure S3.
molecules, both with D3h symmetry. For the trigonal bipyra-
mids, we analyzed AX5(Z) stoichiometries (with A = Si, P, and S Geometry distortions
for the 3rd row, A = Ge, As, and Se for the 4th row, and A = Sn,
Sb, and Te for the 5th row, X = H, F, and Cl, and the pertinent The possibility of inducing core deformations was also ana-
charges, as shown in Table S7 in the Supporting Information). lyzed. First, we investigated the effect of varying the central-
Noteworthy, the ELF maxima in the outer core of the 3rd row atom–ligand distances. Nonetheless, attempts to invert the
atoms have the shape of an inverted triangle (see Figure 4 a core polarization by expanding and compressing the ligand
for PH5). That is, the core localization maxima adopt the shape shell did not lead to core structural changes. This result
of the DP of an equatorial triangle. As for the previous systems, prompted us to analyze the effect of introducing symmetry
this situation inverts when moving to the 4th row atoms, which variations. For this, we substituted one of the ligands in the va-
directly polarize with respect to the valence shell (see Fig- lence shell by a different one. This procedure is represented in
ure 4 b). Thus, the electron pairs in the outer core adopt the Figure 5 a for the transformation of SiF4 into HSiF3. As a conse-
shape of a trigonal bipyramid (EP). Also in agreement with the quence, the molecular geometry evolves from tetrahedral (Td
previous results, the inner cores of the 4th and 5th row atoms symmetry) to trigonal pyramid (C3v symmetry). The geometry
are structured in terms of the EP and DP, as shown in Fig- of the localization maxima in the core was modified according
ure S2. to the variations in the valence shell. In particular, we obtained
the DP of a trigonal pyramid (a distorted tetrahedron), which is
another trigonal pyramid pointing in the opposite direction.
Moreover, we evaluated this effect for 4th row atoms by substi-
tuting silicon by germanium. As expected, the outer core un-
derwent direct polarization, and the electron localization
maxima had the same geometry as the valence shell, that is, a
trigonal pyramid (see Figure 5 a). It is worth noting that this
effect is transferred to the inner core, the localization maxima
of which have the geometry of the DP of the outer core, that
is, another trigonal pyramid. In this way, we show that modifi-
cations and distortions in the valence shell significantly affect
all the core regions.
Another way to induce core modifications by means of ge-
ometry distortions without changing the VSEPR group is by
substituting a ligand by a lone pair (and introducing two more
electrons into the central atom). Figure 5 b shows the evolu-
Figure 4. Outer core polyhedra for: a) PH5, b) AsH5, c) AlH3, and d) GaH3. Hy-
drogen atoms are depicted in light pink, and core ELF maxima in purple. tion of SiF4 to PF3. Note that the lone pair has the same effect
as the ligand variation. Namely, the original tetrahedron in the
core of SiF4 transforms into a trigonal pyramid as a conse-
AX3 stoichiometries
quence of the formal substitution of a fluoride ligand by a
The same principles were shown to hold for the triangular lone pair. The same effect is observed when taking into ac-
molecules AX3(Z) (A = Al and Si for the 3rd row, A = Ga and Ge count 4th and 5th row atoms. For the particular case of the sub-
for the 4th row, and A = In and Sn for the 5th row, with X = H, F, stitution of phosphorus by arsenic, the outer core directly po-
and Cl, and the appropriate charges; see Table S8 in the Sup- larizes towards the valence ligands and the lone pair, forming
porting Information). In the molecular geometries with a cen- the EP, that is, an elongated trigonal pyramid pointing in the
tral 3rd row atom, the outer core counter-polarizes, adopting same direction as the original one. Then, as for the previous
the shape of a trigonal bipyramid with the central vertex op- approach (fluorine substitution by hydrogen), the lone-pair
posed to the valence shell ligands (DP) and the two apical ver- effect in the outer core also influences the inner core, with the
tices perpendicular to the central molecular plane (see Fig- appearance of a complementary elongated trigonal pyramid.

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Figure 5. Evolution of the localization maxima in the core for the transformation of SiF4 into: a) HSiF3 and GeHF3, and b) PF3 and AsF3. Fluoride ligands are de-
picted in blue, lone pairs in orange, and core maxima in purple.

Because the lone pair lacks a core, this shows that the effects
hereby observed are directly related to electron–electron inter-
actions, and not to a crystal field effect arising from the exter-
nal potential (i.e., by the cores of the ligands).

a-Silicon
Motivated by the previous results, we tested the ability of the
model proposed herein to explain the core polarization experi-
mentally determined in a-silicon.[24] The extension of the multi-
polar approximation to the core has shown that the silicon
outer core is polarized in the shape of a tetrahedron, which is
in an inverted position with respect to the tetrahedron formed
by the first coordination sphere. This result is in agreement
with our model, according to which the silicon atom under-
goes counter-polarization with respect to the bonded ligands Figure 6. Model for a-silicon. The second coordination sphere has been re-
(as previously shown for SiX4 geometries, see Figure 3 a). Thus, placed by hydrogen atoms. Silicon in blue, hydrogen in beige, and ELF
the silicon core polarization has the shape of the DP of the va- maxima in pink.
lence ligands, that is, an inverted tetrahedron. To further con-
firm this result, we considered the model system reported in electron pairs. As such, we can observe, for example, a cube as
the original paper, Si(SiH3)4, and analyzed the ELF maxima in a localization pattern for the outer core of the elements of the
the silicon core region.[24] Note that the expected behavior (an 3rd period, which does not lead to two electrons per vertex.
inverted tetrahedron in the silicon core) was observed, as de- For the 4th and 5th periods, the outer-core structure directly
picted in Figure 6. The agreement between the experimental polarizes in the direction of the valence shell polyhedron.
results and the theoretical calculations further supports the Thus, the localization maxima in the core have the shape of
validity of the theory. the direct polyhedron of the ligand shell. This highlights the
softer nature of the core in 4th and 5th row atoms. This concept
of “hard” and “soft” cores is in agreement with the relationship
The model
expected between volume, compressibility, and conceptual
At this point, it may be convenient to summarize the general DFT hardness.[29] Bigger atoms are expected to be easier to
trends that can be derived from the previous results. We have deform and polarize,[30] also leading to less compressible mate-
found that, for the studied systems, all the central elements rials.[31, 32]
(which belong to the same periodic table row) behave equally The coherence of the results support the predictive charac-
in terms of core polarization, independently of the ligands that ter of the polarization model we propose. Hence, it should be
constitute the valence shell. More specifically, in all cases, the possible to predict the core structure of representative ele-
outer core of atoms belonging to the 3rd period undergoes ments just by taking into account the position in the periodic
counter-polarization, and the core localization maxima exhibit table and the coordination number.
the structure of the dual polyhedron of the ligand shell. We in- In this regard, we tested the predictive ability of the model
terpret this behavior to be a consequence of the tendency of by applying it to the structures of three different systems that
the system to minimize repulsive interactions between elec- are not related to those considered for developing the previ-
trons in the valence and the outer-core shell. Note that accord- ous discussion. In particular, we selected XeF4 and [Fe(CN)6]3@,
ing to our results, the core electrons do not necessarily form the core structures of which are shown in Figure 7 a,b (see

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Figure 7. Outer core polyhedra for: a) XeF4, b) [Fe(CN)6]3@, and c) the model system for stishovite (the complete structure for this model is presented in Fig-
ure S4 in the Supporting Information). Core ELF maxima are depicted in purple and lone pairs (LP) in orange.

Table S11 in the Supporting Information for the Cartesian coor- the one considered for the analysis of a-silicon (see Figure S7
dinates).1 The choice of XeF4 was based on the fact that it has and Table S11 in the Supporting Information). Our prediction is
two lone pairs. Thus, this allows us to test whether we can in agreement with the calculation (see Figure 7 c).
extend the results obtained for one-lone-pair systems to those
with more lone pairs. Because xenon belongs to the 5th period,
we would expect direct polarization of the outer core. The mo-
Conclusions
lecular geometry has the shape of a perfect square plus two We have shown that the same physical principles that led to
lone pairs, which together form a compressed octahedron, as the development of VSEPR theory, that is, the molecular geo-
depicted in Figure 7 a. Then, according to the previous results, metries adapting to minimize repulsion between electron
the expected geometry for the outer core is a slightly com- pairs, can be used for predicting the core structure. Moreover,
pressed octahedron, which is the one that was found when we have applied this model to understand in more detail the
performing the calculation (see Figure 7 a). organization of electrons in atoms with several core shells. Two
After that, we attempted to predict the core structure of a different behavior patterns have been identified. On the one
system bearing a transition metal. For that, we selected hand, for nuclei belonging to the 3rd period, the electron locali-
[Fe(CN)6]3@, as a well-known example of a metallic complex for zation maxima in the core orient toward the center of the
which VSEPR theory holds.[33] Because iron belongs to the first- polyhedral faces defined by the valence ligands, so as to mini-
transition-metal row, we expect counter-polarization in the mize electron repulsions. In contrast, for the 4th and 5th periods,
outer core. Thus, taking into account that the molecular geom- several core shells appear, and the outer one orients toward
etry is octahedral, we expect that the localization maxima in the ligands, undergoing direct polarization. This observation
the outer core have the shape of the DP of that octahedron, suggests a pertinent extension of the chemical concepts of
that is, a cube. This hypothesis was checked by performing the hardness and softness to the core region: 3rd row atoms would
calculation, and, effectively, a cube shape was revealed for the be harder than those belonging to the 4th and 5th periods. As a
iron outer core, as shown in Figure 7 b. It is important to note consequence, the spatial disposition of the outer-core elec-
that the main analysis performed in this work was carried out trons of elements belonging to the 3rd period is that that mini-
with main-group elements. Hence, we are wary of extending mizes electron repulsions with the valence electrons. In con-
these trends to systems bearing transition metals, and more trast, the outer core of atoms in the 4th and 5th rows undergoes
systems should be studied to establish general and consistent direct polarization toward the valence shell. In addition, we
trends. have demonstrated that there is an intimate relationship be-
Finally, we checked our ability to predict the core polariza- tween the ligand shell and the core, as valence distortions are
tion in a crystal structure, as a test for crystallographic core po- transferred to all the inner-core shells. Finally, we have shown
larization studies. We selected stishovite, a high-pressure poly- that lone pairs behave as “standard” ligands in terms of core
morph of silica.[34] This system has a tetragonal P42/mnm sym- organization. The principle described herein not only confirms
metry, in which the silicon is in an elongated octahedral coor- the existence of core polarization, but also explains the experi-
dination environment. Then, because silicon belongs to the 3rd mentally found core spatial distributions in a-silicon. Hence,
period, it should counter-polarize with respect to the valence these basic principles can be used to help understand and pre-
shell and the core localization maxima should have the shape dict core polarization in accurate X-ray data.
of an elongated cube (the DP of an elongated octahedron). To
test this prediction, we constructed a cluster model, similar to
Experimental Section
1
Note that the study of these kinds of systems was proposed by one of the re- Geometry optimizations and wave function calculations for ELF
viewers after the development of the initial model. analyses were obtained through DFT calculations by using the

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Gaussian 09 program package.[35] The CAM-B3LYP exchange-corre- [1] W. Thiel, Angew. Chem. Int. Ed. 2011, 50, 9216 – 9217; Angew. Chem.
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structure of the inner core of all the considered elements (up to
[3] R. J. Gillespie, R. S. Nyholm, Q. Rev. 1957, 11, 339 – 380.
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