Dicationic States of Benzene Dimer:

Benzene Dimer Cation and Benzene

Dication Parenthood Patterns
EUGENE S. KRYACHKO
Department of Chemistry, Bat. B6c, University of Liege, Sart-Tilman, B-4000 Liege 1, Belgium and
Bogoliubov Institute for Theoretical Physics, Kiev-143, 03680 Ukraine

Received 25 January 2007; accepted 24 April 2007

Published online 1 June 2007 in Wiley InterScience (www.interscience.wiley.com).
DOI 10.1002/qua.21432

ABSTRACT: High density functional computational levels, B3LYP/cc-pVDZ and

B3LYP/cc-pVTZ, are invoked to study the structural patterns exhibiting between a variety
of the lower-energy conformers of the benzene dimer cation and benzene dication, on one
hand, and the obtuse and acute ground-state conformers of the benzene cation radical, on
the other. In particular, these “obtuse versus acute” patterns for the lowest-energy stable
sandwich structures of the benzene dimer cation, formed due to a strong charge-transfer
resonance interaction between the benzene cation radical as a hole donor and the
ground-state benzene molecule as a hole acceptor benzene dimer cation, are examined
using the molecular orbital analysis and a two-state model. It is shown the existence of
homodimers of the benzene dimer cation composed of equivalent benzene rings,
mimicking either the obtuse or acute conformers of the benzene radical cation, and
representing saddle points on the potential energy surface. The computed potential energy
surface of ionization of the benzene radical cation demonstrates a slight preference of the
triplet state of the benzene dication originated from the obtuse benzene cation over the
singlet which, in contrast, arises from the acute one. The parenthood features of the
benzene dimer cation and benzene dication that appear in the dicationic states of benzene
dimer are discussed. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem 107: 2741–2755, 2007

Key words: dicationic state; benzene dimer; benzene dimer cation; benzene dication;
two-state model

Correspondence to: E. S. Kryachko; e-mail: eugene.kryachko@

ulg.ac.be
The Proceedings of the XI-th Conference “Quantum Systems
in Chemistry and Physics”
Contract grant sponsor: Limburgs Universitair Centrum
(Bijzonder Onderzoeksfonds).
Contract grant sponsor: Region Wallonne.
Contract grant number: RW.115012.
Contract grant sponsor: EC FET-OPEN STREP Project MOL-
DYNLOGIC.

International Journal of Quantum Chemistry, Vol 107, 2741–2755 (2007)

© 2007 Wiley Periodicals, Inc.
KRYACHKO
1. Introduction
B enzene is the most fundamental aromatic mol-
ecule. Its clusters are the simplest prototype
systems with π/π interactions that are important in
many areas of chemistry and biology [1]. The neutral
benzene clusters and the benzene dimer in particular
were the focus of numerous experimental and the-
oretical studies [2] (see also note [3]1 ). The benzene
dimer admits the two most stable and nearly isoen-
ergetic slipped-parallel and T-shape π -structures. In
contrast, much less studies have been conducted on
charged clusters of benzene (C6 H6 )Z+ n (n ≥ 1) [4].2
The simplest systems in this series are the benzene
cation radical (n = 1, Z = 1, n + Z = 2) recently
drawn a particular attention as a typical Jahn-Teller
system [5], benzene dimer cation (n = 2, Z = 1), and
benzene dication (n = 1, Z = 2).
The benzene dimer cation and benzene dica-
tion are the basic elements in the studies of
doubly-charged benzene clusters which are origi-
nated from multiple ionization processes and often
undergo the energetic dissociation that is well-
known as Coulomb explosion [6]. It has recently
been demonstrated that in contrast to monomers,
doubly-charged clusters behave fundamentally dif-
ferent under inner-valence ionization. This behavior,
referred to as the intermolecular Coulomb decay
[6], is simply explained by that the double ion-
ization threshold in clusters is lowered relative to
the isolated monomer since two holes in the for-
mer can be spatially separated via localizing on
different monomers, thus reducing their hole–hole
Coulomb repulsion and decreasing the double ion-
ization threshold. The hole–hole Coulomb repulsion
is usually rather strong and therefore, the dicationic
1 The neutral benzene dimer is predominantly a van der Waals
complex. As though, the B3LYP/cc-pVDZ and B3LYP/cc-pVTZ
computational levels used in the present work also predict two
stable and nearly isoenergetic parallel displaced and T-shaped
structures of the neutral benzene dimer (precisely, the former has a
tiny imaginary frequency of 3 ı cm−1 which is within the computa-
tional margin), we cannot be confident with their estimates of the
corresponding interaction energies. This is due to the well-known
deficiency of many density functionals to significantly under-
estimate the dispersion interaction, even to predict it as being
repulsive. However, for the charged dimers, electrostatic and
covalent interactions are the dominant contributions to the inter-
action energy, and therefore, the aforementioned computational
levels are rather accurate.
2 There is no evidence of an existence of negatively charged
benzene clusters in the gas phase. Notice that in the gas-phase
electron affinity of the ground-state benzene molecule is negative,
EAa (C6 H6 ) = −1.12 eV.
2742 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
state of a given small cluster lies higher the corre-
sponding monocation species. That is why a doubly-
charged cluster is “Coulombically” exploded.
It is intuitively clear that there might exist some
critical size nc (Z+ ) of a multiply charged cluster of
charge Z+ , composed of n molecules, such that if
n(Z+ ) < nc (Z+ ), the fission into two charged frag-
ments is more favorable and, on the contrary, if
n(Z+ ) > nc (Z+ ), a rather high Coulomb repulsion
barrier renders a given cluster rather substantial life-
time [7]. Asimple estimation of the critical size nc (Z+ )
of a given cluster is provided by the liquid drop
model (LDM) which resembles the model of the
Coulomb instability of liquid droplets proposed in
1882 by Lord Rayleigh [8] and developed by Meitner
and Frisch [9], and Bohr and Wheeler [10]. According
to the LDM [11–13], nLDMc (Z+ ) is obtained by equating
the electrostatic energy Z2 /R of a charged sphere of
radius R with Z positive charges to its surface energy
γ R2 where γ is the surface tension. This yields the
critical radius RcLDM (Z+ ) equal to (Z2 /γ )1/3 and hence
implies that nLDMc (Z+ ), as being proportional to the
volume of the sphere, scales as Z2 .
Despite the crudeness of the LDM, its estimate
nLDM
c (Z+ ) provides a quite reasonable lower bound to
expt
the experimental value nc (Z+ ) available for many
multiply charged van der Waals (vdW) clusters: a
given vdW Z+ -charged cluster of size n that obeys
the inequality n  nc is intrinsically unstable and its
fragmentation is exothermic [11–13].
For benzene, the LDM predicts nLDM c (C6 H6 ; 2+ ) =
18 (see Table II of Ref. 12a) which is comparable with
expt
nc (C6 H6 ; 2+ ) = 23 [14] (see particularly Fig. 2
expt
of Refs. 13 and 15). nc (C6 H6 ; 2+ ) suggests that
the benzene dimer dication may exist in the gas
phase as the vdW cluster of 21 benzene molecules
mediating two terminal benzene cation radicals.
These 21 benzene molecules “soften” the mutual
Coulomb repelling of two positively charged ben-
zene cations and prevent the entire cluster to be
Coulomb exploded.
The validity of the LDM, which only accounts for
electrostatic effects to explain the relative stability of
multiply charged atomic or molecular clusters and
rather crudely assumes that, first, the excess charge
(hole) spreads over the entire cluster surface and sec-
ond, that the constituting molecules are arranged in
a manner to minimize the total surface energy, has
been debated for a long time. The recent work [16]
has provided a strong computational evidence for
the existence of a novel class of the kinetically sta-
ble, long-lived dicationic states of benzene clusters
(C6 H6 )+2
n (n ≥ 2; see Fig. 1 for n = 2) and small dica-
DOI 10.1002/qua VOL. 107, NO. 14
 DICATIONIC STATES OF BENZENE DIMER

FIGURE 1. The B3LYP/T lower-energy portion of the potential energy surface (PES) of (C6 H6 )2+
2 (right) and the
structure (left) of the long-lived dicationic state of the benzene dimer with a fused interring C C bond. The low-energy
asymptote is 2 C6 H+ 6 ( B2g ) and the upper one is C6 H6 + C6 H6 ( B1g ).
2 2+ 3

tionic assemblies of benzene, hexafluorobenzene,
and naphthalene. Their existence that lies beyond
the LDM’s grasp unequivocally demonstrates that
a newly formed C(sp3 ) C(sp3 ) interring bond at the
expense of cyclic π-conjugation surpasses the strong
Coulomb repulsion, normally prevailing between
charged monomers, and produces a rather high
Coulomb barrier (Fig. 1) to confer a substan-
tial kinetic stability to covalently fused dicationic
clusters.
The parent species of the dicationic states of ben-
zene dimer, the benzene dimer cation (C6 H6 )+ 2 , and
benzene dication C6 H2+ 6 are the main theme of the
present study. It is demonstrated that their struc-
tural patterns originate from the obtuse and acute
ground-state conformers of the benzene cation rad-
ical. The computational methodology invoked for
this purpose is outlined in the next section.
2. Computational Framework
All computations reported in the present work
were performed with the hybrid density functional
B3LYP potential using the GAUSSIAN 98 pack-
age of programs [17]. The Dunning’s correlation
consistent polarized valence bases of double- and
triple-zeta quality cc-pVDZ (≡ D) and cc-pVTZ (≡ T)
[18] were employed to perform all geometry opti-
mizations with the default integration grid. The
symmetry constraints were not imposed. The com-
putational levels B3LYP/cc-pVDZ (B3LYP/D) and
B3LYP/cc-pVTZ (B3LYP/T) are known to be ade-
quate for the geometry optimization and vibrational
frequencies of such species as benzene cation and
benzene dimer cation (vide Refs. 3, 5e and refer-
ences therein). The analytical harmonic vibrational
frequencies and corresponding zero-point vibra-
tional energies (ZPVE) were calculated at the both
computational levels in order to topologically dis-
tinguish the stationary structures. Enthalpies and
entropies were also estimated from the partition
functions calculated at room temperature under a
pressure of 1 atm, using Boltzmann thermostatistics
and the rigid-rotor-harmonic-oscillator approxima-
tion. The expectation value of the S2 operator for
radicals was obtained equal to 0.750. The natural
bond orbital (NBO) analysis was performed for some

VOL. 107, NO. 14 DOI 10.1002/qua INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 2743
KRYACHKO
FIGURE 2. The S- and D-sandwiches of (C6 H6 )+2 in its ground electronic state. Their selected B3LYP/T distances are
given in Å. Their optimized geometrical parameters are collected in Table I. Notice that the benzene rings of the S- and
D-sandwiches are skewed relative to each other, viz., in the S-sandwich by ≈8◦ (∠C3 C6 C9 C12 = 172.2◦ and in the D-one
by ≈11◦ (∠C5 C2 C8 C11 = 11.2◦ ).
selected lower-energy conformers of the benzene
dimer cation.
3. Benzene Dimer Cation - Ionization
of Benzene Dimer
3.1. GROUND-STATE SANDWICH STRUCTURES
The benzene dimer cation (C6 H6 )+ 2 has been exten-
sively studied during the last four decades, mainly
on the experimental side [19–24]. The enthalpy Hf
of its formation from the ground-state benzene mol-
ecule and benzene cation radical estimated by means
of several experimental techniques ranges from −8
to −21 kcal mol−1 [19a–e].
The structure of (C6 H6 )+
2 has been for a long time a
rather controversial issue [19–21]. Initially, i has been
suggested that its ground state represents a symmet-
ric sandwich of a D6h symmetry with two parallel
and perfectly superimposed benzene ring [11a, 12c].
This structure has been later ruled out as the global
energy minimum in favor of the displaced sand-
wich [21d] and T-shape [19f] ones. The displaced-
sandwich model of (C6 H6 )+ 2 relies on the existence
of at least two sandwich-type structures [21c] max-
imizing the charge-transfer resonance interaction
C6 H+ +
6 · C6 H6 ⇔ C6 H6 · C6 H6 [19(a, d), 20(c, e)]. It has
also been invoked to interpret its photodissociation
2744 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
spectra revealing four peaks at 2.82, 2.14, 1.35, and
1.07 eV [21]. On the other hand, pump-probe hole-
burning experiments have demonstrated that if the
T-shape structure of (C6 H6 )+2 would exist, its rela-
tive population is smaller compared to that of the
sandwich [21f]. The full geometry optimization of
relaxed benzene rings, recently carried out by means
of the CASSCF, MRSDCI, and MRCPA methods [20j],
reveals the existence of two different sandwichlike
structures, one corresponds to the slipped (S-) C2h -
sandwich and the other to the distorted (D-) C2v one
(Fig. 2).
The S- and D-sandwiches are characterized by
anticlockwise ordering of the C C bond lengths
within their two rings (vide Table I and Fig. 2). Struc-
turally, each ring of the S-sandwich has four longer
(≥1.40 Å) and two shorter (1.377 Å) C C bonds com-
pared to the neutral benzene molecule3 . In contrast,
each ring of the D-sandwich has four C C bonds
whose lengths are smaller than 1.40 Å and the two
longer ones (≥1.41 Å). These structural patterns of
the S- and D-sandwiches resemble those pertaining
to the two nearly energetically equivalent isomers
3 The ground-state neutral benzene molecule is characterized
by the following B3LYP/T geometry [5e]: r(C C) = 1.391 Å,
r(C H) = 1.082 Å, and ∠C6 C1 C2 = ∠C1 C2 H2 = 120◦ .
DOI 10.1002/qua VOL. 107, NO. 14
 DICATIONIC STATES OF BENZENE DIMER

TABLE I
The bond lengths (in Å) and bond angles (in ◦ ) of the lower-energy structures on the PES of the ground
electronic state of the benzene dimer cation radical.
S-sandwich D-sandwich TS1 TS2 Acute homodimer Obtuse homodimer
Geometry B3LYP/D B3LYP/T B3LYP/D B3LYP/T B3LYP/D B3LYP/D B3LYP/D B3LYP/T B3LYP/D B3LYP/T

r(C1 C2 ) 1.386 1.377 1.427 1.419 1.389 1.397 1.395 1.387 1.416 1.408
r(C1 H1 ) 1.091 1.081 1.092 1.081 1.092 1.092 1.091 1.080 1.092 1.082
r(C2 C3 ) 1.413 1.404 1.405 1.397 1.417 1.422 1.426 1.419 1.385 1.377
r(C2 H2 ) 1.091 1.081 1.092 1.081 1.092 1.092 1.092 1.081 1.091 1.081
r(C3 C4 ) 1.411 1.404 1.388 1.379 1.409 1.397 1.395 1.387 1.416 1.408
r(C3 H3 ) 1.092 1.082 1.091 1.080 1.092 1.092 1.092 1.081 1.091 1.081
r(C4 C5 ) 1.386 1.377 1.422 1.415 1.389 1.397 1.395 1.387 1.416 1.408
r(C4 H4 ) 1.091 1.081 1.092 1.081 1.092 1.091 1.091 1.080 1.092 1.082
r(C5 C6 ) 1.421 1.412 1.402 1.393 1.417 1.422 1.426 1.419 1.385 1.377
r(C5 H5 ) 1.091 1.081 1.092 1.082 1.092 1.092 1.092 1.081 1.091 1.081
r(C1 C6 ) 1.420 1.412 1.390 1.382 1.409 1.397 1.395 1.387 1.416 1.408
r(C6 H6 ) 1.091 1.080 1.091 1.081 1.092 1.092 1.092 1.081 1.091 1.081
r(C7 C8 ) 1.386 1.377 1.427 1.419 1.385 1.385 1.395 1.387 1.416 1.408
r(C7 H7 ) 1.091 1.081 1.092 1.081 1.091 1.091 1.091 1.080 1.092 1.082
r(C8 C9 ) 1.420 1.412 1.390 1.382 1.410 1.410 1.426 1.419 1.385 1.377
r(C8 H8 ) 1.091 1.080 1.091 1.081 1.091 1.091 1.092 1.081 1.091 1.081
r(C9 C10 ) 1.421 1.412 1.402 1.393 1.423 1.422 1.395 1.387 1.416 1.408
r(C9 H9 ) 1.091 1.081 1.092 1.082 1.091 1.092 1.092 1.081 1.091 1.081
r(C10 C11 ) 1.386 1.377 1.420 1.415 1.384 1.384 1.395 1.387 1.416 1.408
r(C10 H10 ) 1.091 1.081 1.092 1.081 1.091 1.091 1.091 1.080 1.092 1.082
r(C11 C12 ) 1.411 1.404 1.388 1.379 1.412 1.413 1.426 1.419 1.385 1.377
r(C11 H11 ) 1.091 1.081 1.091 1.080 1.091 1.091 1.092 1.081 1.091 1.081
r(C7 C12 ) 1.413 1.404 1.405 1.397 1.424 1.424 1.395 1.387 1.416 1.408
r(C12 H12 ) 1.092 1.082 1.092 1.081 1.090 1.090 1.092 1.081 1.091 1.081

The atomic labels are shown in Figure 2.

of the benzene cation radical C6 H+ 4 2

6 : its obtuse B2g
conformer structurally mimics each benzene ring of
the former sandwich, whereas the acute 2 B1g one is
similar to each ring of the latter one. This suggests
the existence of two symmetry-constrained routes
of the formation of the S- and D-sandwiches of
(C6 H6 )+
2:
C6 H+ +
6 ( B2g ) + C6 H6 ( A1g ) → S-sandwich (C6 H6 )2
2 1
C6 H+ 2 1 +
6 ( B1g ) + C6 H6 ( A1g ) → D-sandwich (C6 H6 )2 .
(1)
4 Recall that the D
2h obtuse (compressed) and acute (elon-
gated) conformers of C6 H+
6 have four equal and two equal
shorter or longer C C bonds, respectively [5]. The B3LYP/T bond
lengths of the obtuse and acute structures of C6 H+ 6 are the fol-
lowing [5e]: (i) obtuse: r(C1 C2 ) = r(C3 C4 ) = r(C4 C5 ) =
r(C1 C6 ) = 1.426 Å, r(C2 C3 ) = r(C5 C6 ) = 1.365 Å; (ii) acute:
r(C1 C2 ) = r(C3 C4 ) = r(C4 C5 ) = r(C1 C6 ) = 1.384 Å,
r(C2 C3 ) = r(C5 C6 ) = 1.448 Å. There exists a tiny difference
in energy of 8 cm−1 [5c] between the obtuse and acute structures
of the benzene radical cation.
The S- and D-sandwiches are almost isoener-
getic. The S-sandwich is slightly more stable, viz.,
by 169 cm−1 (100 cm−1 after ZPVE) at the B3LYP/D
computational level. The B3LYP/T reduces this
energy offset to 133 cm−1 (66 cm−1 after ZPVE;
cf. 0.1 kcal mol−1 in Ref. 20j). The ZPVE-corrected
binding energies Eb (S) and Eb (D) of the S- and D-
sandwiches defined by means of Eq. (1) amount
correspondingly to 16.57 and 16.38 kcal mol−1
(B3LYP/T) and are within the experimental range
of 17.07 ± 1.50 kcal mol−1 [24a] and 17.99 kcal mol−1
[21g]. The enthalpies of formation of the S- and
D-sandwiches at 298 K equal to −15.56 (S) and
−15.36 (D) kcal mol−1 are also concurred with the
experimental estimates.
Additionally, some noteworthy computational
data regarding the S- and D-sandwiches are gath-
ered in Tables II and III. For example, their
B3LYP/T isotropic hyperfine Fermi constant cou-
plings (HFCC) are presented in Table II. As partic-
ularly shown therein, the average hydrogen HFCCs
of both sandwiches fall within the experimental
range reported by Itagaki et al. [20i]. Table III

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KRYACHKO

TABLE II
The isotropic hyperfine Fermi constant coupling (HFCC, in MHz) of the two lowest-energy structures of the
benzene dimer cation radical calculated at the B3LYP/T computational level.

Geometry S-sandwich D-sandwich Acute homodimer Obtuse homodimer

C1 −3.65 −0.10 −8.52 4.45

C2 −6.62 +4.33 1.05 −5.44
C3 +5.02 −6.65 1.05 −5.44
C4 −6.95 −2.84 −8.52 4.45
C5 −3.28 +3.67 1.05 −5.44
C6 +6.72 −9.12 1.05 −5.44
C7 −3.64 +4.33 −8.52 4.45
C8 −6.64 −0.10 1.05 −5.44
C9 +5.03 −9.12 1.05 −5.44
C10 −6.94 +3.67 −8.52 4.45
C11 −3.29 −2.84 1.05 −5.44
C12 +6.72 −6.65 1.05 −5.44
H1 −4.11 −9.01 1.88 −13.79
H2 −0.18 −10.29 −9.80 −1.95
H3 −13.20 +0.16 −9.80 −1.95
H4 +0.20 −4.64 1.88 −13.79
H5 −4.56 −12.48 −9.80 −1.95
H6 −10.40 +2.14 −9.80 −1.95
H7 −0.17 −10.29 1.88 −13.79
H8 −4.13 −9.01 −9.80 −1.95
H9 −10.39 +2.14 −9.80 −1.95
H10 −4.54 −12.48 1.88 −13.79
H11 +0.18 −4.64 −9.80 −1.95
H12 −13.21 +0.16 −9.80 −1.95
Hav −5.38 (−6.39a ) −7.40 (−6.39a ) −2.01 −5.90
Expt. [20i] −6.03–−6.27

The atomic labeling follows Figure 2. Notice that the HFCCs of the obtuse structure of the benzene cation radical are equal to 9.56
MHz (C1 and C4 ), −9.88 MHz (C2,3 and C5,6 ), −3.87 MHz (H2,3 and H5,6 ), and −27.93 MHz (H1 and H4 ).
a Indicates the average over two given sandwiches. The experimental data [20i] refer to different temperatures and to different matrices

CFCl3 and CF3 CCl3 .

collects the vibrational spectra of both sandwiches C 6 H+

and compares them with those of the ground-state
neutral benzene molecule, and the obtuse and acute
structures of the benzene cation radical. Inspecting
this Table, it is worth to draw attention to a highly
IR active C C stretching mode originated from the
mode 8 of benzene. It is centered at 1607 cm−1 for the
S-sandwich and characterized by IR activity of 1314
km mol−1 . This mode is assigned to the symmetric
coupled C C stretch of the shortest bonds, C1 C2 ,
C4 C5 , C7 C8 , and C10 C11 (Fig. 2) and red-shifted
by 65 cm−1 relative to the same mode of the obtuse
structure of C6 H+6 due to the delocalization of charge
over two rings in (C6 H6 )+ 2 . In the D-sandwich, this
mode is less IR active (819 km mol−1 ) and peaked
at 1583 cm−1 , thus slightly blue-shifted relative to
the corresponding mode of the acute structure of
6 . Its dominant contribution originates from
the coupled C C stretches of the shortest C C
bonds.
3.2. THE ORIGIN OF SANDWICH STATES OF
BENZENE DIMER CATION
It has been demonstrated in the previous Sub-
section that the benzene dimer cation (C6 H6 )+ 2
admits two most energetically stable conformers,
the slipped and distorted sandwiches. Their bind-
ing energies are 7–8 times larger the binding energy
of the neutral benzene dimer, that naturally arises
due to a strong charge-transfer (CT) resonance inter-
action between C6 H+ +
6 as a hole donor in (C6 H6 )2
and C6 H6 as a hole acceptor. The CT resonance
interaction holds the excess charge (hole) equally

2746 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.1002/qua VOL. 107, NO. 14
 DICATIONIC STATES OF BENZENE DIMER

TABLE III
The vibrational modes of the neutral benzene (within Wilson’s nomenclature [25]), benzene radical cation in the
lowest-energy states of the 2 B2g (obtuse) and 2 B1g (acute) symmetries and benzene dimer cation radical in its
lowest-energy sandwich-type states.

Benzene Bz+ (2 B2g ) Bz+ (2 B1g ) Bz2+ (S-sandwich) Bz2+ (D-sandwich)

Mode sym Expt. [25c] Theor. [5e] Theor. [5e] Theor. [5e] Theor. Theor.

1 δ(CCC) a1g 993.071 1031 1018 1017 1038 (2) 1039 1104 (6) 1170
2 ν(C H) a1g 3073.942 3193 3217 3218 3214 (22) 3215 3212.0 (24) 3213.0
3 δ(C H) a2g 1350 1390 1374 1360 1365 (19) 1370 1364 (7) 1370 (9)
4 γ (CCC) b2g 707 727 421 395 639 (4) 640 631 (4) 632
5 γ (C H) b2g 990 1015 979 977 1065.1 1065.5 (6) 1036 1037 (2)
6 δ(CCC) e2g 608.13 624 234 290i 377 (1) 383 561 (2) 574
517 (3) 581
604 606 604 (120) 615 602 (105) 616
7 ν(C H) e2g 3056.7 3168 3193 3195 3194.4 3194.9 3191.1 3191.5
3203 3200 3195.3 3195.6 3202.0 (1) 3202.8
8 ν(C C) e2g 1600.976 1637 1398 1398 1536 (31) 1537 1534 (26) 1539
1672 1579 1607 (1314) 1650 1583 (819) 1626 (1)
9 δ(C H) e2g 1177.776 1200 952 917 1192.5 1193.4 1192 (47) 1194 (2)
1222 1207 1204 (184) 1211 1198 (131) 1209
10 γ (C H) e1g 847.1 868 800 857 844 845 (1) 852 856 (1)
913 879 890 902 (4) 891 (2) 894 (1)
11 γ (C H) a2u 673.9746 692 (104) 687 (86) 687 (86) 708.6 (1) 708.8 (135) 704 (98) 708 (6)
12 δ(CCC) b1u 1010 1022 1047 1038 985 (303) 996 986 (221) 999
13 ν(C H) b1u 3057 3158 3190 (2) 3191 (1) 3186.7 3187.0 3184.6 3184.8
14 ν(C C) b2u 1309.4 1335 1548 (48) 1475 (187) 1394.4 1394.6 1395.7 1395.9
15 δ(C H) b2u 1149.7 1177 1206 1206 (3) 1139 (9) 1156 1069 (3) 1073
16 γ (CCC) e2u 398 414 292 (3) 305 377 (1) 383 372 374
346 334 (4) 385 391 386 389
17 γ (C H) e2u 967 989 1014 (5) 1020 1003 1011 1006.9 1007.5 (1)
1033 1026 (4) 1038 (2) 1039 1018.6 1018.9
18 δ(C H) e1u 1038.267 1062 (5) 964 (29) 954 (19) 1022.0 1022.5 1017.6 (2) 1018.2 (1)
1071 (11) 1095 (5) 1027.7 1028.1 (4) 1025.0 1025.5
19 ν(C C) e1u 1483.985 1519 (8;3) 1402 (35) 1398 (8) 1461 (4) 1488 1439 (1) 1487 (100)
1461 (116) 1536 (19) 1489 (2) 1491 (52) 1495 (3) 1515 (6)
20 ν(C H) e1u 3064.367 3183 (39;39) 3207 (9) 3203 (9) 3206.8 3207.0 3202.0 3202.8
3215 (16) 3216 (19) 3214 (22) 3215 3207.2 3207.5

All computed frequencies are referred to the B3LYP/T level. Frequencies are given in cm−1 and nonzero IR activities (in parentheses)
in km mol−1 .

delocalized over their two benzene rings [5, 19(a, f),
20c, 23d, 24(a, b)]. These sandwiches may be there-
fore classified as Mulliken charge-transfer com-
plexes [26]. While they are formed, the hole, initially
localized on the π spin-up lowest unoccupied molec-
ular orbitals (LUMO↑s) of the obtuse or acute con-
formers of C6 H+ 6 , partially migrates to the highest
occupied molecular orbital (HOMO) of the neutral
benzene molecule. This is schematically displayed in
Figure 3.
It is assumed that the hole through-space trans-
fer is favorable if the HOMO of benzene is the πy
for the S-sandwich and πx for the D. A closeness of
the MO energies of these LUMO↑s, εLUMO↑obtuse
= −7.25
eV and εLUMO↑ = −7.27 eV, to the εHOMO
acute benzene
= −7.03
eV, guaranties a rather efficient intradimer HOMO–
LUMO charge transfer. A theoretical ansatz based
on the two-state model of C6 H6 and C6 H+ 6 [26, 27] is
proposed below.
Let us assume a validity of a two-state ansatz for
C6 H6 and C6 H+ 6 [26,27]. The ground-state wavefunc-
tions of the CT S- and D-sandwiches can be then
represented as symmetrized Hartree products of the
two group wave functions (see particularly Ref. 27a,

VOL. 107, NO. 14 DOI 10.1002/qua INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 2747
KRYACHKO

depending on a partition of the studied (2N − 1)-

electron dimer into the cationic and neutral parts
governed by the sub-Hamiltonians H1+ (H2+ ) and H2o
(H1o ), respectively. V and V  are the total intradimer
Coulomb interaction operators whose difference (in
atomic units), V ≡ V −V  = [ i=1 N−1
− i=N+1
2N−1
]1/riN −
[ α=1
M
− α=M+1
2M
]Zα /rNα , describes the electron-hole
and hole-nuclear Coulomb interactions (the sub-
script α = 1, . . . , M = 12 refers to the α-th nucleus
characterized by the radius vector Rα and the nuclear
charge Zα ; rij = | ri − rj |, and riα = |ri − Rα|).
Within the ansatz (2), the corresponding binding
energies of the S- and D-sandwiches are explicitly
FIGURE 3. The MO picture of the formation of the S-
given as
and D-sandwiches of (C6 H6 )+
2 . The upper MO is the
HOMO of C6 H6 , whereas the lower is the LUMO↑ of the
     
obtuse and acute structures of C6 H+
6 , correspondingly, −Eb (S) ≡ +S |H|+S − φ1+obtuse H1+ φ1+obtuse 1,2,...,N−1
for the S- and D-sandwiches.
    
+ φ1o H2o φ1o N,N+1,...,2N−1
Section 2–16 and also Refs. 21c, 21h for a single
1
sandwich), = [Iobtuse + IIobtuse + IIIobtuse
2(1 + SS )

 1 1
+S {ri }2N−1
i=1 =√ + IVobtuse ] + εobtuse (4)
2(1 + SS ) 2
 +obtuse
N−1  o
2N−1 
× φ1 {ri }i=1 φ2 {ri }i=N and

 +obtuse


+ φ1 {ri }N
o
i=1 φ2 {ri }2N−1      
− Eb (D) ≡ +D |H|+D − φ1+acute H1+ φ1+acute 1,2,...,N−1
i=N+1

    

 1 + φ1o H2o φ1o N,N+1,...,2N−1
+D {ri }2N−1
i=1 =√
2(1 + SD ) 1
 +acute
N−1  o
2N−1  = [Iacute + IIacute + IIIacute
× φ1 {ri }i=1 φ2 {ri }i=N 2(1 + SD )

 +acute
2N−1  1
+ φ1o {ri }N + IVacute ] + εacute (5)
i=1 φ2 {ri }i=N+1 . (2) 2
In Eq. (2), φ1o ({ri }N i=1 ) and φ2 ({ri }i=1 ) are the ground-
o N
where

. . .L,L+1,...,L+K indicates the integration over

and first-excited state normalized wave functions the L, L + 1, . . . , L + K electrons and εx ≡ (ε2o − ε1o ) −
of C6 H6 with the corresponding eigenenergies ε1o (ε2+x − ε1+x ). In Eqs. (4) and (5), the matrix elements
and ε2o . φ1+x ({ri }N−1 +x
i=1 ) and φ2 ({ri }i=1 ) are those of the
N−1
of the Coulomb interaction operators V and V  are
+
x-structure of C6 H6 (x = obtuse, acute) character- designated as:
ized by the eigenenergies ε1+x and ε2+x . SS and SD
 
are the overlap integrals defined correspondingly Ix ≡ φ1+x φ2o | V | φ1+x φ2o
as
φ1+obtuse φ2o | φ1o φ2+obtuse  and
φ1+acute φ2o | φ1o φ2+acute ;  
N = 42, and the spins are henceforth omitted. The IIx ≡ φ1o φ2+x | V  | φ1o φ2+x
 
contributions of the wave functions of the obtuse IIIx ≡ φ1+x φ2o | V | φ1o φ2+x
conformer of C6 H+ 6 to + and that of the acute one
S
 
to + are worth noticed.
D IVx ≡ φ1+x φ2o | V  | φ1o φ2+x = IIIx + εx . (6)
The total electronic Hamiltonian H of (C6 H6 )+ 2
casts as The charge-resonance energy of the X-sandwich
(X = S or D) is defined as the energy difference,
H = H1+ (1, . . . , N − 1) + H2o (N, . . . , 2N) + V ECTX , between the first excited and ground states
of the X-sandwich. Within the ansatz (2), the first-
= H1o (1, . . . , N) + H2+ (N + 1, . . . , 2N − 1) + V  (3) excited state wave function is written as (see in

2748 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.1002/qua VOL. 107, NO. 14
 DICATIONIC STATES OF BENZENE DIMER

particular Ref. 27a, Section 2–16 and also Refs. 20c, arises due to the difference of the last three terms
20h for a single sandwich) for the S- and D-sandwiches, particularly, to that of
the Coulomb integrals Ix and IIx given by Eq. (6).

 1  +x
N−1  o
2N−1  Concluding, this ansatz provides the explicit for-
−X {ri }2N−1
i=1 =√ φ1 {ri }i=1 φ2 {ri }i=N mulas for Eb (S) and Eb (D), and also some estimates
2(1 − SX )
of the energy differences, ECT X , between the first

 +x
2N−1 
− φ1o {ri }N excited and ground states of each sandwich, thus
i=1 φ2 {ri }i=N+1
determining their charge-resonance energies.
(x = obtuse (X = S), acute (X = D)). (7)

Obviously, −X is orthogonal to +X . One then explic-
itly obtains
1
ECT = [(Ix + IIx )SX − (IIIx + IVx )].
X
1 − S2X
ECTX is the energy separation between the peaks
of the +X → −X CT absorption transition [26, 27].
Two CT resonance bands at 920 nm (1.35 eV) and
at 1,160 nm (1.07 eV) were experimentally observed
for the benzene dimer cation [20(b–d), 22(a)] (cf.
Eq. (5) in Ref. 20c). Interestingly, if the overlap inte-
grals SX  1, ECTX is strongly determined by the CT
integrals,
ECT
X = −(IIIx + IVx ) = −(2IIIx + εx ).
Nevertheless, the above assumption of smallness of
the overlap integrals SS and SD is not fully valid
in the present case of the S- and D-sandwiches as
rather strong CT dimers whose interring distances
are shorter (especially in the contact regions) than
the sum of van der Waals radii for C6 H6 and C6 H+ 6.
Finally, neglecting εx , one obtains from Eq. (9) that
ECT
X
−2IIIx . (10)
Within the assumption SX  1, one readily derives
from Eqs. (4) and (5) that
1 Both benzene rings in the obtuse and acute cationic
Eb (X) = −IIIx − εx − (Ix + IIx )
2 homodimers are nearly parallel to each other. In the
1
CT  1
= EX − εx − (Ix + IIx ).
2 2
CT,expt CT,expt
Comparing ES = 1.35 eV and ED = 1.07
eV with Eb (S) = 0.72 eV and Eb (D) = 0.71 eV,
one concludes that the first term, ECT X /2 on the
rhs of the last equation in (11) provides the domi-
nant contribution to the binding energies of the S-
and D-sandwiches. Therefore, within the ansatz (2),
the difference between their CT resonance bands,
estimated experimentally as being equal to 0.28 eV,
3.3. LOW-ENERGY PORTION OF PES
OF BENZENE DIMER CATION
In Figure 4 we picture the lower-energy portion
(8) of the PES of (C6 H6 )+
2 which include the obtuse and
acute cationic homodimers having an approximate
D2h symmetry. By a direct analogy with the corre-
sponding parent structures of the benzene cation
radical [5], the former is a first-order saddle struc-
ture with the imaginary transition frequency of 29 ı
cm−1 , whereas the latter is a second-order one with
two imaginary transition frequencies of 186 ı and
26 ı cm−1 . Only 244 cm−1 (B3LYP/T; 301 cm−1 at
B3LYP/D) separate the acute homodimer from the
S-sandwich. The obtuse homodimer lies only 3 cm−1
(4 cm−1 ; precisely speaking these energy differ-
(9)
ences are within the error margins of the employed
computational methods) below the acute one at the
B3LYP/D (B3LYP/T) level, although the inclusion of
ZPVE correction reverses this order and places the
acute one below by 39 cm−1 (103 cm−1 ).
Structurally, the four shorter C C bonds of each
benzene ring in the acute homodimer are slightly
elongated (by 0.003 Å), whereas the two longer ones
are contracted quite substantially (by 0.029 Å), as
compared to the acute C6 H+ 6 benzene cation radical
(see footnote 4) (vide Table 1). A similar geometri-
cal pattern holds for the obtuse homodimer, viz., its
four longer C C bonds are contracted by 0.010 Å
whereas the two shorter are elongated by 0.010 Å.
acute one, for example, the B3LYP/cc-pVTZ inter-
(11) ring distances between the carbon atoms bonded via
two short C C bonds are slightly larger (3.572 Å)
compared to that between the carbon atoms sharing
the short and long C C bonds (3.546 Å). Moreover,
the hydrogen atoms in this homodimer are slightly
pulled out (by 0.022–0.023 Å) of the benzene interior
region. It is worth mentioning that the NBO charges
of both homodimers indicate that the hole is equally
delocalized over two rings. Their transition modes
distort such interring disposition.

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KRYACHKO

FIGURE 4. The lower-energy section of the potential energy surface of the electronic ground state of (C6 H6 )+2 . The
ZPVE-corrected energies are indicated in parentheses. The superscripts D and T correspond to the B3LYP/D and
B3LYP/T computational levels, respectively. The equilibrium geometries of the displayed structures are given in Table IV.

FIGURE 5. The B3LYP/cc-pVTZ picture of ionization of the benzene cation radical. The superscript ∗ indicates the
ZPVE-uncorrected vertical ionization energies.

2750 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.1002/qua VOL. 107, NO. 14
 DICATIONIC STATES OF BENZENE DIMER

TABLE IV
The B3LYP/T electronic energy E (in hartree), ZPVE (in kcal mol−1 ), enthalpy H (in hartree), and entropy S
(in kcal mol−1 K−1 ) of the benzene cation and dicationic structures.

Bz+ (2 B1g ) 1 Bz2+ 3 Bz2+ 3 Bz2+

ts Bz+ (2 B2g ) 1 Bz2+
saddle=3
1 Bz2+
saddle=2
1 Bz2+
ts1
1 Bz2+
ts2

E + 231 −0.998846 −0.434007 −0.437225 −0.436961 −0.998995 −0.413117 −0.413311 −0.418875 −0.424546
ZPVE 60.72 60.20 60.43 60.28 61.30 58.83 58.86 60.23 59.15
H + 231 −0.897373 −0.333041 −0.334661 −0.336022 −0.896119 −0.315163 −0.314607 −0.317812 −0.325438
S 68.91 71.41 73.57 70.76 70.68 66.09 70.60 71.19 69.59

It is worth finally mentioning the existence of two
T-skewed first-order saddle structures, TS1 and TS2 ,
and the perfect T-shape second-order saddle struc-
ture S2 (T) of C2 symmetry on the PES of (C6 H6 )+ 2.
The transition-state linker TS1 to the S-sandwich is
placed 3.40 kcal mol−1 higher (B3LYP/D). The other
saddle structure TS2 related to the D-one lies 2.91
kcal mol−1 above it. The B3LYP/D optimized geome-
tries of these saddle structures are collected in Table I.
Notice that by analogy with the S-sandwich, both
rings of TS1 have two shorter and four longer C C
bonds compared to those of benzene. While a similar
C C bond pattern holds for the upper ring of TS2 ,
its lower one resembles the D-sandwich.
4. Benzene Dication - Double
Ionization of Benzene Molecule
The benzene dication C6 H2+ 6 is the simplest dica-
tion in the series of doubly charged benzene clusters.
True, it has the important and longstanding practical
value as itself (see, e.g., Refs. 28–31 and references
therein). Experimentally, C6 H2+ 6 has been detected
under ionization of benzene in intense laser fields
[32–34]. In the charge-separation processes [29], the
benzene dication fragments into the cations C5 H+
3
and CH+ 3 [35] (see also Refs. 36, 37). The correspond-
ing kinetic energy release amounts to 2.6–2.8 eV
[35] implying that the intercharge distance reaches
≈5.1–5.5 Å [38], that is almost twice as large as the
C C diameter (≈2.9 Å) of the ground-state neutral
benzene molecule.
Almost four decades ago [38], the benzene dica-
tion was treated as an open structure. Regrettably, the
experiments on charge stripping and charge strip-
ping/charge exchange were unable to provide any
structural information on this molecular species [37]
(see also Ref. 39)—this was actually the reason why
it has been for a long time considered as a “diffi-
cult system” whose structure and properties have
remained “considerably less known” [37]. Later, in
the eighties [31,37,39], contrary to the early view, the
benzene dication was regarded as being structurally
“the same as neutral benzene” [37]. This is one side
of this story.
The other one is that the benzene molecule is char-
acterized by at least 226 doubly ionized states which
span within an electron binding energy range of 23–
40 eV [41]. In contrast to its first ionization that yields
the benzene cation radical C6 H+ 6 which exists either
as the 2 B2g (obtuse) state or the 2 B1g (acute) one (see,
e.g., Ref. 5 and references therein), its double one
exhibits a rather complex pattern first reported in
the present work and displayed in Figure 5 (see also
Table IV). As shown in particular in Figure 5, the
vertical ionization of each ground-state conformer
of C6 H+ 6 leads to two structures, singlet or triplet
(B3LYP/T):
singlet
IEv (Bz+ : 2 B2g (obtuse) ⇒ 1 B2g )
= 16.13 eV, IEv
triplet
(Bz+ : 2 B2g (obtuse) ⇒ 3 B2g )
= 15.47 eV;
singlet
IEv (Bz+ : 2 B1g (acute) ⇒ 1 B1g )
triplet
= 16.12 eV, IEv (Bz+ : 2 B1g (acute) ⇒ 3 B1g )
= 15.47 eV.
The above values of the vertical ionization ener-
expt
gies fairly agree with the experimental IEv (Bz+ ) =
16.2 eV [42], that was determined from the charge
stripping data, and the early computational ones,
IEtheor (Bz+ ) = 16.10 (singlet) and 15.47 (triplet) eV5
v
(B3LYP/6-311G(d,p) calculations [28]; cf. with the
upper boundary of 17.16 eV [43]).
A simple comparison of the reported vertical ion-
ization energies of C6 H+ 6 indicates that the triplet
states of C6 H2+ are energetically favorable by about
6
5 Similarly to Ref. [30], it is worthwhile mentioning that a small
discrepancy between the experimental and theoretical ionization
energies might arise due to Franck-Condon effects in vertical
ionization.

VOL. 107, NO. 14 DOI 10.1002/qua INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 2751
KRYACHKO

TABLE V
The B3LYP/T structures of the benzene dication.

Bz+ (2 B1g ) 1
Bz2+ 3
Bz2+ 3
Bz2+
ts Bz+ (2 B2g ) 1
Bz2+
saddle=3
1
Bz2+
saddle=2
1
Bz2+
ts1
1
Bz2+
ts2

r(C1 C2 ) 1.384 1.388 1.424 1.426 1.426 1.470 1.468 1.381 1.432
r(C2 C3 ) 1.448 1.457 1.424 1.426 1.365 1.351 1.351 1.535 1.373
r(C1 H1 ) 1.080 1.084 1.087 1.087 1.083 1.091 1.092 1.084 1.099
r(C2 H2 ) 1.082 1.097 1.087 1.087 1.081 1.085 1.085 1.088 1.089
∠C6 C1 C2 118.4 107.2 119.7 120.0 121.6 123.3 123.1 117.0 125.2
∠C1 C2 H2 120.6 119.1 120.1 120.0 119.4 118.8 119.1 121.6 122.3

The atomic labels are indicated in Figure 6. Bond lengths are given in Å and bond angles in ◦ (Ref. 23 for the geometry of the ground
electronic state of the neutral benzene molecule).

0.5 eV over the singlets (see also Refs. 28, 44). Tak-
ing into account the first vertical ionization energy
of benzene of 9.24 eV [5] evaluated at the B3LYP/T
level, the double vertical ionization energy thus
amounts to 24.72 eV (triplet) and 25.27–25.36 eV
(singlet). Note that the B3LYP/6-311G(d,p) yields
correspondingly 25.55 and 24.50 eV [28] and the
photoionizationation threshold value is 25.3 eV [44]
and 26.0 eV [30] (the B3LYP/6-31G(d,p) estimate is
25.4 eV [45]).
However, as we observe in Figure 5, four verti-
cally ionized states of C6 H2+6 are relaxed in a dras-
tically different way. While the singlet state, that
is originated from C6 H+ 2
6 ( B2g ; obtuse), transforms
adiabatically into the planar third-order saddle
structure 1 Bz2+ 2
saddle =3 ( B2g ), characterized by the tran-
sition frequencies of 1159 ı, 509 ı, and 79 ı cm−1
(see Table V), the other, arised from the acute
benzene cation radical, directly relaxes to the sin-
glet energy minimum structure 1 Bz2+ characterized
by the ZPVE-corrected adiabatic ionization energy
singlet
IEa (Bz+ : 2 B1g (acute) ⇒ 1 B1g ) = 15.35 eV (the
B3LYP/6-311G(d,p) method yields 15.36 eV [30]).
1
Bz2+ has a planar carbon ring with four short C C
bonds (1.388 Å) and the two longer ones (1.457
Å; vide Figure 6 and Table V) implying that this
singlet state of C6 H2+ 6 is structurally close to the
acute benzene cation radical rather than to the neu-
tral benzene. The longer C C bonds have longer
C H bonds (1.097 Å) lying out of the ring plane

FIGURE 6. The B3LYP/cc-pVTZ singlet- and triplet-state structures, 1 Bz2+ and 3 Bz2+ of the benzene dication C6 H2+
6 .
Their bond lengths are given in Å and bond angles in ◦ (some geometrical parameters of the parent obtuse C6 H+ 2
6 ( B2g )
and acute C6 H+6 ( 2
B 1g ) structures of the benzene cation radical, calculated at the same computational level [5e], are
presented in Table V).

2752 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.1002/qua VOL. 107, NO. 14

(the dihedral angle ∠H2 C2 C3 H3 = 48.0o ) in order
to reduce the mutual Coulomb repulsions. Interest-
ingly, the obtuse-type branch of the relaxation route
also ends at the acute-like structure 1 Bz2+ of the
singlet-state benzene dication (vide Fig. 6).
The triplet structure 3 Bz2+ resulted from ioniza-
tion of Bz+ (2 B2g ; obtuse) is the energy minimum
of C6 H2+ 6 . The relevant ZPVE-corrected adiabatic
triplet
ionization energy IEa (Bz+ : 2 B2g (obtuse) ⇒
3
B2g ) amounts to 15.25 eV (cf. with the B3LYP/6-
311G(d,p) value of 15.28 eV [28]). Figure 6 and
Table IV demonstrate that 3 Bz2+ is characterized
by almost equal C C bonds (1.424 Å). Its nonpla-
narity arises due to a small out-of-ring disposition
of the four hydrogen atoms bonded to C2 , C3 , C5 ,
and C6 (the dihedral angle ∠H2 C2 C3 H3 = 9.8◦ ).
The triplet ionization route started from the acute
benzene cation radical involves the transition-state
linker 3 Bz2+ ts ( B1g ) with the transition frequency of
2
−1
1941ı cm and ends at the same triplet state 3 Bz2+
triplet
(IEa (Bz+ : 2 B1g (acute) ⇒ 3 B2g ) = 15.29 eV) as the
ionization route originated from the obtuse struc-
ture of C6 H+ 6 . 0.06 eV determines a difference
between the adiabatic ionization energies corre-
sponding to the singlet and triplet ionization routes
of the benzene cation radical and thus indicates a
slight preference of the triplet-state benzene dication
over its singlet state. However, this small difference
falls within the range of chemical computational
accuracy [46].
5. Summary and Conclusions
In the present work, invoking the B3LYP/D and
B3LYP/T computational methods, we have demon-
strated that the benzene dimer cation only admits
two lowest-energy sandwiches of the S- and D-types.
Their origins have been explained in terms of the par-
ent obtuse and acute structures of the benzene cation
radical. Two novel acute and obtuse homodimers
of (C6 H6 )+
2 have been found in a close proximity
of the S- and D-sandwiches. It will be shown else-
where that they determine the barrier shown in
Figure 1 that confers a substantial kinetic stability to
covalently fused dicationic cluster of benzene dimer.
All studied T-shaped-like structures of the benzene
dimer cation, including the perfect T-shaped one,
lie on a rather flat portion of the PES that prevents
the precise identification of their saddle structure
features.
We have thoroughly investigated the computed
PES of ionization of the benzene cation radical in
VOL. 107, NO. 14 DOI 10.1002/qua INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
DICATIONIC STATES OF BENZENE DIMER
all its structural motifs. It has been demonstrated
that the ionization route of the obtuse benzene cation
radical directly yields the lowest triplet state of the
benzene dication, whereas the singlet state originates
from that of the acute conformer. A small preference
of 0.06 eV (see also Ref. 31d, p. 1050 and Ref. 31g, p.
1194) predicted at the B3LYP/T computational level
for the benzene dication to finally occupy the most
stable triplet state rather than the singlet one has
been reported. In contrast to the longstanding belief,
neither the singlet state nor the triplet one of the
benzene dication structurally resemble the neutral
ground-state benzene molecule.
In conclusion, we have unveiled the importance
of the “obtuse versus acute” structural motif of the
benzene cation radical underlying the structural pat-
terns that are exhibited on the low-energy portions
of the PESs of the benzene dimer cation and benzene
dication.
ACKNOWLEDGMENTS
The author gratefully thanks Lenz Cederbaum for
lively and fruitful discussions, Francoise Remacle,
Jean-Pierre Francois, and Michael Deleuze for warm
hospitality.
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