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Evolution of structure and properties of neutral and

Cite this: Dalton Trans., 2013, 42, 8644 negatively charged transition metal–coronene
complexes: a comprehensive analysis†
Li-Ping Ding, Xiao-Yu Kuang,* Peng Shao and Ming-Min Zhong

Received 24th February 2013,
Accepted 26th March 2013
DOI: 10.1039/c3dt50499a
www.rsc.org/dalton
The geometries, electronic and magnetic properties of neutral and negatively charged Mn(coronene)m
(M = V and Ti; n, m = 1, 2) complexes were investigated using density functional theory. The results show
that one V or Ti atom prefers to occupy the η6-site in M(coronene)0/− complexes and to be sandwiched
between the two coronene molecules in M(coronene)20/− complexes. Two metal atoms always form a
dimer and interact with one coronene molecule. The calculated vertical electron affinities and transition
energies are in good agreement with experimental values. This lends considerable credence to the
obtained ground state structure and validates the chosen computational method. The bond formation
between metal atom and coronene is accounted for by 3d/4s–π bonds, as revealed by the molecular orbi-
tals plots. The reason why the peripheral ring site binds metal most effectively has been analyzed system-
atically by π electron content, aromaticity and average charge on carbon atoms. The electron localization
function shows that there is perfect electron delocalization in these complexes. Furthermore, the mag-
netic moments of V(coronene)0/− and Ti(coronene)− are found to be substantially enhanced over the cor-
responding free metal atom; the magnetic moment of the neutral Ti(coronene) remains unchanged;
while the larger size clusters experience a reduction.

1. Introduction subject have been investigated extensively. The results show

Organometallic complexes with various aromatic molecular
ligands exhibit unusual bonding which has fascinated chem-
ists over the past years.1 Recently, the potential applications of
metal–organic complexes as building blocks of novel magnetic
material have renewed interest in organometallic complexes.
In particular, transition metal (TM)–organic complexes have
attracted considerable interest because of the wide variety of
their structural and magnetic properties. It is well known that
TM clusters have larger per atom magnetic moments than in
their corresponding bulk state.2 Moreover, these magnetic
properties can be further modified when TM atoms are sup-
ported on organic molecules. Therefore, identifying combi-
nations of TM atoms and organic supports would be a
significant step toward discovering building blocks for novel
magnetic materials.
The potential applications of TM–organic complexes have
stimulated numerous experimental3–14 and theoretical6,9,11,12–15
studies. In particular, TM–benzene complexes12–14 as a typical
Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065,
China. E-mail: scu_kuang@163.com; Fax: +86 28 85405515
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c3dt50499a
that TM–benzene complexes can form either a sandwich struc-
ture or a so-called “rice-ball” structure. With the development
of gas phase cluster experiments, more and more numerous
new systems emerge. For example, TM bound to polycyclic aro-
matic hydrocarbons (PAHs)5,6,16–22 have been described in
molecular beam experiments and mass spectrometry. Multi-
decker sandwiches and other network structures have been
proposed for some of these systems. Although many of these
new π-complex clusters have never been isolated, their struc-
ture and bonding properties are nonetheless interesting. This
interest is based on the fact that these PAHs are good essential
structural elements of graphite and large diameter carbon
nanotubes for studying the interaction with metal clusters.
Coronene (C24H12), the smallest PAH, with six benzene rings
fused to a central six-member ring, is large enough to afford
multiple binding sites for metal attachment on its surface.
Interior or exterior rings are available for π bonding on one or
both sides of the organic surface. This may be lead to a variety
of metal–coronene multidecker complexes with unique struc-
tural and magnetic properties. Thus, metal–coronene com-
plexes have become the focus of experimental and theoretical
investigation.
From an experimental point of view, TM–coronene cationic
complexes were first reported in the gas-phase by Dunbar and

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co-workers.23 Their results showed that the complexes reacted
readily and formed TM(coronene)2 complexes. Buchanan
et al.20 have studied positively charged Fem(coronene)n (m =
1–3, n = 1, 2) complexes by laser vaporizing. The results
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greater than they are for the isolated metal cluster or coronene
molecule? (3) What are the bonding properties of Mn(corone-
ne)m0/− (M = V and Ti; n, m = 1, 2) complexes? (4) Which kind
of ring (central versus peripheral) site might bind metal most

showed that Fe forms a strong covalent bond with the PAH
surface and can form stable sandwich structures. The multi-
metal and multidecker sandwich structures were also con-
firmed by the investigation of Crm(coronene)n+ (m = 1–5, n =
1–3) complexes.24 On the theoretical front, the density func-
tional theory (DFT) investigation of Fem(coronene)n0/+ com-
plexes20 provided a different view of structures, which
indicated that Fe2 dimerizes and forms a strong bond with cor-
onene. Kandalam et al.15 studied the structure and properties
of Com(coronene)n complexes and compared the results with
iron–coronene complexes. They found that both the Co atom
and dimer prefer to occupy η2-bridge binding sites and the
magnetic coupling of Co–Co atoms remains ferromagnetic.
In the present study, we are interested in investigating new
examples of metal–PHA complexes in the form of vanadium–
coronene and titanium–coronene clusters. To the best of our
knowledge, Duncan et al.25 have reported the anion photo-
electron spectroscopic data, in which vanadium–coronene and
titanium–coronene complexes were produced by laser vapori-
zation techniques. Based on this experiment, the author found
that the EA values are greater for the organometallic complexes
than that of the isolated metal clusters or coronene molecule.
V(coronene)2 complexes exhibit different spectra under
different conditions, suggesting two possible structural con-
figurations. They also predicted that Ti(coronene)2 does not
form a sandwich structure, but forms a coronene dimer with
metal atom binding externally to one of the coronene mole-
cules. But no direct structural information on these complexes
can be obtained from this experiment. While the structures
and energetics of these complexes are particularly interesting
issues that should be addressed by theory. Unfortunately, we
are not aware of any earlier theoretical studies on Vn(corone-
ne)m and Tin(coronene)m. Motivated by the absence of theoreti-
cal efforts on these complexes, we have initiated a systematic
theoretical study. Here, there are several basic issues that we
hope to address. (1) What are the geometric structures of these
complexes? (2) Whether the EA values of these complexes are
effectively? (5) How are the magnetic moments of V and Ti
atoms modified in going from free atom to the complexes?
Additionally, we also assessed the similarity and difference
between Vn(coronene)m and Tin(coronene)m complexes.
2. Computational detail
The electronic structure calculations of both neutral and nega-
tively charged TM–coronene complexes (Vn(coronene)m and
Tin(coronene)m, n, m = 1, 2) were carried out in the framework
of the density functional theory (DFT) method, using the
GAUSSIAN 03 program.26 The exchange-correlation functional
PBE27 according to the approach proposed by Perdew, Burke,
and Ernzerhof was adopted. The split-valence double-ξ basis
set (6-31+G) was adopted for transition metal (V and Ti) atoms
and the coronene molecule. The reliability and accuracy of the
functional form and basis set was first guided by extensive
tests performed on two-atom clusters (V2 and Ti2), using a
variety of functionals (PW91,28,29 B3PW91,28–30 B3LYP,28,31
BP86,31,32 TPSS,27 PBE and wB97XD33) and basis sets
(LanL2DZ,34 CEP-121G,35,36 6-311+G,37 6-31+G38 and
6-31+G*39). The tested results were compared with the experi-
mental values and are summarized in Tables 1 and 2, respecti-
vely. It can be seen that the bond length and frequency of the
vanadium (V2) and Titanium (Ti2) based on the PBE/6-31+G
level are in good agreement with the experimental values.40,41
In order to further validate the selected method and basis set,
we performed a test on the vertical electron affinities (VEAs)
for coronene using various functionals and basis sets. The
results, which are listed in ESI Table S1,† also encouraged us
to select the PBE/6-31+G level. Furthermore, the VEAs of the
TM–coronene complexes were calculated at this level and com-
pared with the corresponding measured values.22,25,42,43 These
calculated results, which are listed in Table 3, are in excellent
agreement with early experimental values. This increased the

Table 1 Results for the vanadium dimer (V2) at different levels

Methods

Parameter Basis set PW91 B3PW91 B3LYP BP86 TPSS wB97XD PBE Exp.

Bond length/Å Lanl2dz 1.780 1.748 1.754 1.780 1.784 1.733 1.781 1.77038
CEP-121G 1.779 1.747 1.753 1.780 1.775 1.731 1.781
6-311+g 1.777 1.659 1.748 1.777 1.779 1.724 1.778
6-31+g 1.782 1.748 1.755 1.780 1.784 1.733 1.780
6-31+g* 1.737 1.630 1.643 1.739 1.743 1.685 1.739
Vibrational frequency/cm−1 Lanl2dz 657 714 707 659 655 726 654 53838
CEP-121G 638 691 685 639 636 703 635
6-311+g 630 790 677 631 631 670 627
6-31+g 641 695 689 642 653 708 638
6-31+g* 664 839 810 664 659 755 660

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Table 2 Results for the titanium dimer (Ti2) at different levels

Methods

Parameter Basis set PW91 B3PW91 B3LYP BP86 TPSS wB97XD PBE Exp.
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Bond length/Å Lanl2dz 1.933 1.903 1.912 1.934 1.936 1.954 1.938 1.94339
CEP-121G 1.941 1.829 1.857 1.943 1.936 2.000 1.947
6-311+g 1.929 1.897 1.834 1.931 1.936 1.891 1.936
6-31+g 1.936 1.909 1.920 1.938 1.947 1.903 1.944
6-31+g* 1.891 1.862 1.808 1.893 1.903 1.857 1.897
Vibrational frequency/cm−1 Lanl2dz 473 522 519 473 483 448 467 40939
CEP-121G 448 541 481 449 468 368 443
6-311+g 441 494 537 441 444 552 444
6-31+g 442 492 493 442 440 534 435
6-31+g* 469 522 582 469 464 566 459

Table 3 The calculated vertical electron affinities (eV) for the neutral pure 3. Results and discussions
metal, coronene and metal–coronene clusters studied here and compared with
the experiment values Based on the method that has been pointed out above, a
EA (Mn) EA (Mn–coronene) EA (Mn–coronene2)
number of optimized isomers for neutral and negatively
charged Mn(coronene)m (M = V and Ti; n, m = 1, 2) clusters
Species Theo Exp Theo Exp Theo Exp were obtained. The most stable structure and one of the low-
b lying isomers are presented in Fig. 1 and 2. Some other
V=0 0.54 0.54 ± 0.1 0.59 0.67 ± 0.09c
V=1 0.535 0.525a 1.33 1.38 ± 0.07a 0.81 0.91 ± 0.14a isomers together with their information are listed in the ESI
V=2 0.521 0.522d 1.16 1.12 ± 0.06a (Fig. S1 and S2†). For the Vn(coronene)m clusters, the nomen-
Ti = 1 0.174 0.079a 1.15 1.31 ± 0.06a 1.19 1.28 ± 0.06a
clature of the neutral isomers are designated by N-nma and
Ti = 2 0.668 1.35 1.53 ± 0.13a
N-nma1, …; the anions are designated by A-nma and A-nma1.
a
Ref. 25. b Ref. 42. c Ref. 22. d Ref. 43. For the Tin(coronene)m clusters, the nomenclature of the
neutral isomers are designated by N-nmb and N-nmb1, …; the
anions are designated by A-nmb and A-nmb1, where n rep-
confidence in the reliability of our selected computational resents the number of M atoms, and m represents the number
method. of coronene molecules in the Mn(coronene)m clusters. The cal-
The coronene (C24H12) molecule has two different types of culated electronic state, point symmetry and relative energy for
carbon rings: one carbon ring (termed as the peripheral ring) each structure are also shown in these figures. Additionally,
shares four carbon atoms with three other rings, while the for some negatively charged complexes, the photodetachment
other type of carbon ring (termed as the central ring) shares transition energies from a spin multiplicity (2S + 1) change of
six carbon atoms with six other carbon rings. So the polycyclic ±1 were calculated and are presented in Fig. 3. The calculated
character of the coronene molecule offers a wide variety of magnetic moment for each cluster is listed in Table 5.
binding sites for the metal atom. In the geometry optimization
procedure, four-types of structures were considered for TM–
coronene complexes containing one coronene molecule (site 3.1 Geometries
on top of central/peripheral rings (η6), various C–C bridge sites 3.1.1 Geometric structures of Vn(coronene)m0/− (n, m = 1, 2)
(η2) between the central and peripheral rings, between two per- V(coronene) and V(coronene)−. The photoelectron spectrum
ipheral rings, and on the edge of the peripheral rings). Two- of the complex V(coronene)− was measured by Duncan and co-
types of structures were considered for TM–(coronene)2 com- worker.25 It is dominated by a strong peak centered at approxi-
plexes (sandwich and nonsandwich structures) to identify mately 1.5 eV binding energy. The strong sharp feature
their ground state geometry. All the geometry optimization cal- suggests that there is a vertical transition with minimal geo-
culations were carried out without any symmetry constraint. In metrical change between the anion and the neutral complex.
addition, different possible spin multiplicities were also taken They also inferred that V(coronene) is a π complex with the
into account for each of these isomers. In order to determine metal located in a η6 ring site, and the neutral and anion clus-
that the optimized geometry corresponds to a local minimum ters have similar structures.
in potential energy, each of them was followed by an analysis Our theoretical calculations reveal that the V atom in
of the harmonic vibrational frequencies. Furthermore, the VEA neutral V(coronene) complex prefers to occupy the on-top site
of the neutral complex was calculated as the energy difference (η6) on the peripheral ring of coronene. This result well sup-
between the optimized neutral and the anion at optimized ports the Duncan group’s inference. The high spin state (2S +
neutral geometry. The transition energies (VDEs) of some 1 = 6) is the most preferred spin state. When an electron is
anion isomers were also computed and analyzed. added to the V(coronene) complex, we found that the structure

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Fig. 1 Optimized structures of neutral Mn(coronene)m (M = V and Ti; n, m = 1, 2) complexes.

Fig. 2 Optimized structures of anionic Mn(coronene)m− (M = V and Ti; n, m = 1, 2) complexes.

remained relatively unchanged. The ground state structure of
V(coronene)− has point group symmetry (Cs) and electronic
state (5A′′). The distance between the metal atom and the top
of coronene plane shortened from 1.78 Å (neutral isomer) to
1.62 Å (anion). This may be due to the fact that the attachment
of an extra electron enhances the interaction between the
metal atom and coronene molecule. If the structure is
restricted in the other types (e.g. V atom/anion located on
various C–C bridge η2-site or η6-site above the center ring)
during the geometry optimization process, the V atom moves
away from the other sites to the η6-site above the peripheral
ring. Namely, no matter where we place the V atom it always

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Fig. 3 Transition energies from the ground state of the anion Ti(coronene)−
and V2(coronene)− complexes to the corresponding neutral species having the
same geometry as the anion, but with spin multiplicities changing of ±1.
tries to go into the η6-site of the peripheral ring. This is con-
sistent with previous NMR spectroscopy analysis44 which pre-
dicted that metal π bonding in a peripheral ring site is
perhaps more likely than it is for the central site. Why the per-
ipheral ring site is more favorable for binding metal than the
central ring will be discussed in section 3.4.
V2(coronene) and V2(coronene)−. We now discuss the results
of the interaction of two V atoms with one coronene molecule.
In both neutral and anionic forms, we have considered various
structural configurations, in which two V atoms bind both
associatively (dimer like) and dissociatively (atom like) to
various binding sites on the surface of a coronene molecule.
For the ground state structure of neutral V2(coronene) (Fig. 1),
the V2 dimerizes and prefers binding to the η2 C–C edge
shared between two adjacent peripheral rings. The V–V bond
length (1.78 Å) in this configuration is identical to that of the
pure V2 dimer. Note another neutral conformation (N-21a2),
which is shown in Fig. S1,† is only 0.036 eV higher in energy
than the lowest energy structure. These two structures are
almost degenerate in energy. In order to ensure the accuracy of
the calculations, we have performed DFT computations with
PW91 and BP86 functionals. The calculated results (see
Table 4) based on three methods show that the N-21a isomer
has a lower energy than that of N-21a2. Namely, the preferred
ground state was retained, independently of the theoretical
method. Furthermore, the calculated VEA for this ground state
N-21a isomer is 1.16 eV, which is in excellent agreement with
the measured value (1.12 ± 0.06 eV).25 In the N-21a1 isomer,
both of the two V atoms occupy the η2-site on the two adjacent
peripheral rings, with the dimer bond axis almost parallel to
Table 4 Comparison of the relative energies (eV) between the energetically
very close isomers with PBE, PW91 and BP86 methods for V2(coronene)
Isomers PBE PW91 BP86
N-21a 0.000 0.000 0.000
N-21a2 0.036 0.043 0.061
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the coronene molecule. The V–V bond length (2.18 Å) in this
isomer is elongated compared to that of the lowest energy
isomer (1.78 Å). The spin multiplicity of the two isomers was
calculated to be 2S + 1 = 1.
The ground state V2(coronene)− complex (A-21a), in which
the two V atoms occupy the bridge sites of a peripheral ring,
has a 4A electronic state. The isomer A-21a1, which is 0.25 eV
higher in energy than the ground state, has a similar structure
with the neutral lowest-energy isomer. Additionally, some
other structures were observed in our optimization, such as
A-21a3 and A-21a4 isomers, in which the bond axis of the V2
dimer is almost perpendicular to the coronene molecule. Only
one V atom directly interacts with coronene via the bridge site
(η2) of the peripheral ring or the two adjacent peripheral rings.
This is similar to the structures of Co2(coronene)− and Fe2(cor-
onene)− complexes in reported previously.15,43 According to
the above discussions, we conclude that the V atoms always
form a dimer and interact with the coronene molecule. This
result is in agreement with the earlier prediction.15
V(coronene)2 and V(coronene)2−. Duncan and co-worker have
analyzed the two possible structures (sandwich and nonsand-
wich) of the V(coronene)2 complex under different conditions
(a) coronene was vaporized first, and (b) metal was vaporized
first. The results showed that the sandwich isomer was formed
predominantly under both conditions and has a significantly
lower EA than the nonsandwich isomer. In our structural
optimization, three different structural configurations were
considered. The first was a normal sandwich structure, in
which vanadium atom and coronene molecules were arranged
alternately. The second one was a staggered sandwich struc-
ture in which one of the coronene planes was rotated some
angle with respect to the other ring. The third was a nonsand-
wich structure. The results showed that the most stable struc-
ture of the neutral V(coronene)2 is a staggered sandwich
structure (N-12a), with the V atom sandwiched between two
coronene molecules (Fig. 1). The two coronene molecules have
only one peripheral ring overlapped and are linked by the
metal atom. Note that the coronene planes are parallel to each
other. The spin multiplicity and electronic state of this isomer
are 2S + 1 = 2 and 2A, respectively. The sextet nonsandwich
isomer N-12a1 is 2.39 eV higher in energy than the ground
state. Coronene molecules form a dimer with the V atom
binding externally to one of the coronene molecules. The two
coronene molecules are parallel to each other and steplike.
Additionally, another sandwich structure N-12a3 (Fig. S1†) was
also obtained. The V atom binds to the η6-bridge sites on the
peripheral rings of one coronene and the central ring of the
other coronene molecule. Our optimized results provide evi-
dence for the existence of sandwich and nonsandwich struc-
tures for V(coronene)2 complexes and validate Duncan’s
prediction.25
For the anion V(coronene)2− complex, the geometries (see
Fig. 2 and Fig. S1†) were also found to be sandwich and non-
sandwich structures. Unlike the neutral V(coronene)2, for the
sandwich structure, the terminal carbon ring of the upper
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Dalton Transactions
coronene molecule, which is linked to the metal atom, is
rotated by 30° with respect to that of the bottom coronene
molecule.
3.1.2 Geometric structures of Tin(coronene)m0/− (n, m = 1, 2)
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Ti(coronene) and Ti(coronene)−. The ground state structure of
the Ti(coronene) complex is a triplet spin state (2S + 1 = 3)
with Cs symmetry, in which the Ti atom prefers to occupy the
C–C η2-bridge site on the peripheral ring of the coronene mole-
cule. The geometry of N-11b1 corresponds to Ti occupying the
η6-on-top site of the peripheral ring and is 1.11 eV higher in
energy than the ground state. Similar to the V(coronene)−
complex, the ground state of Ti(coronene)−, in which the Ti
atom occupies the η6-site of the peripheral ring, has Cs point
symmetry. The distance of Ti atom above the peripheral ring
of coronene plane is 1.92 Å, which is longer than that of
V(coronene)−. This suggests that the interaction of Ti–C is
weaker than that of V–C.
Ti2(coronene) and Ti2(coronene)−. According to the exper-
iment,25 a similar pattern in the spectra of Ti2(coronene)− and
V2(coronene)− was observed implying that the two systems are
expected to share similar geometrical structure. Just as the dis-
cussion on V2(coronene), the Ti atoms in Ti2(coronene)0/− also
dimerize and interact with the coronene molecule. Moreover,
the common structural feature among these isomers is that
both the Ti atoms are directly bound to the coronene molecule
and always have η2-coordination. For the isomer N-21b3 (see
Fig. S2†), the Ti atoms occupy the η2-bridge sites of the
peripheral ring and directly interact with the coronene mole-
cule. In addition, two other structures (see N-21b4, and N-21b5
in Fig. S2†) in which the Ti2 dimer occupies the η6-binding
site of the peripheral or central ring were also found for
Ti2(coronene)0/− complexes. While these two structures were
not found for V2(coronene)0/−.
Ti(coronene)2 and Ti(coronene)2−. Similar to V(coronene)2,
the lowest energy structure of Ti(coronene)2 is a staggered
sandwich structure. The two coronene planes are rotated away
from one another, leaving one terminal ring on top of the
other but not exactly overlapping. This is not consistent with
the earlier experimental prediction25 that the Ti(coronene)2
exists primarily as an external metal isomer and not as a sand-
wich. This sandwich isomer closely resembles the shape of the
V(coronene)2− anion complex but is different from the neutral
V(coronene)2. The spin multiplicity is calculated to be a singlet
state. In addition, the nonsandwich structure (N-12b1) in
which the Ti atom is bound to the η2-bridge site of the periph-
eral ring in the upper coronene molecule is also obtained.
For anionic Ti(coronene)2−, the lowest energy structure is
very similar to that of neutral Ti(coronene)2 in terms of how
the Ti atom is staggered between two coronene molecules and
how the Ti sits on the top of a terminal ring (η6) of each coro-
nene. During the geometrical optimization procedure, two
different nonsandwich structures were found. One is an abnor-
mal nonsandwich structure in which the two coronene mole-
cules are almost located on the same plane but the opposite
end of the coronene molecule is opened up; the other one is a
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normal nonsandwich. The two different structures may
depend on the spin multiplicity.
3.2 Comparison of the theoretical predictions and
experimental spectra
To further discern whether our obtained most stable structure
could account for the photoelectron spectrum, we have calcu-
lated the VEAs of neutral complexes and compared the results
with experimental values. The calculated VEAs, measuring the
difference in ground state energy of the neutral complex and
the anion having the ground state geometry of the neutral
complex, for each cluster size are shown in Table 3. As shown
in the table, it is interesting to find that the corresponding
metal–coronene complexes have significantly greater VEA value
than the pure metal atom/dimer and coronene molecule.
Additionally, we also find that those values are in good agree-
ment with the measured values. This not only answers the
second question of our paper, but also lends considerable cre-
dence to the obtained ground state structure for neutral
isomers. While for the negatively charged Ti(coronene)− and
V2(coronene)− complexes, there is a low-lying isomer here
which is energetically very close to the ground state isomer,
respectively. Since a small energy difference makes it difficult
to distinguish between them or possibly indicate the existence
of both isomers in the beam. Thus, their photodetachment
transition energies (VDEs) from a spin multiplicity (2S + 1)
change of ±1 are calculated and presented in Fig. 3. By com-
paring the VDE with peaks in the experimental spectrum (see
ESI Fig. S3†), one should, in principle, be able to distinguish
between two isomers.
Duncan’s group25 has measured the photoelectron spec-
trum and VDE (approximate 1.5 eV) for Ti(coronene)− which is
similar to that of V(coronene)− (see V(coronene)− spectrum in
Fig. S3†). Our theoretical calculation revealed that the VDEs of
A-11b from the anion quartet to the neutral triplet and quintet
are 1.51 and 1.36 eV, respectively. The higher transition energy
1.51 eV agrees well with the measured value. The first VDEs of
A-11b1 are 2.12 eV (anion doublet to neutral singlet) and
1.14 eV (anion doublet to neutral triplet), which do not agree
with the experimental value. These results lead us to conclude
that the A-11b is really the ground state isomer in the present
DFT calculations.
As for the anionic V2(coronene)− complex, Fig. S3† shows
the experimental photodetachment transition as well as the
calculated VDEs. As mentioned above, the ground state of the
V2(coronene)− anion is a quartet spin state. The calculated
transition energies of the quartet isomer A-21a are 1.38 and
1.73 eV, corresponding to the transitions from the anion
quartet to the neutral triplet and quintet states, respectively.
The transition energies of the doublet isomer A-21a1 were cal-
culated to be 1.41 eV (anion doublet to neutral singlet) and
1.54 eV (anion doublet to neutral triplet). Comparing these
transition energies with the measured BE values in the range
of 1.5 to 1.75 eV, it appears that the two isomers all contribute
to the first peak (about 1.63 eV) of the photoelectron spectrum.
However, in the case of the second peak centered at about
Dalton Trans., 2013, 42, 8644–8654 | 8649

Paper
1.72 eV, the calculated VDE for the quartet isomer is in better
agreement than the doublet isomer. Therefore, we conclude
that only the lowest energy quartet isomer is generated more
favorably in the V2(coronene)−, although an amount of doublet
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isomer seems to coexist.
3.3 Bonding properties of Mn(coronene)m0/− (M = V and Ti;
n, m = 1, 2) complexes
The nature of bonding between metal atom and coronene
molecule in Mn(coronene)m0/− (M = V and Ti; n, m = 1, 2) com-
plexes are manifested by their molecular orbitals (MOs) plots.
Their HOMOs (highest occupied molecular orbitals) with bond
signatures between the 3d/4s electrons of metal atom and the
π-cloud of coronene are shown in Fig. 4 and 5. Additionally,
Fig. 4 The HOMOs of the ground state structures of Vn(coronene)m0/−. The first column corresponds to the α highest occupied molecular orbitals, while the second
corresponds to the β HOMOs.
Fig. 5 The HOMOs of the ground state structures of neutral and negatively charged Tin(coronene)m. The first column corresponds to the α highest occupied mol-
ecular orbitals, while the second corresponds to the β HOMOs.
8650 | Dalton Trans., 2013, 42, 8644–8654
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Dalton Transactions
their HOMO − 1 and HOMO − 2 are also shown in ESI Fig. S4
and S5† to probe further the nature of bonding. As seen from
the HOMO of the dimer V(coronene) in Fig. 4, the HOMO(α) is
a bonding orbital having bonding characteristics between the
dxz of vanadium atom and the π orbital of coronene. While the
HOMO(β) clearly presents the π orbital with the mixed dz2 of V
atom. The spin-up HOMO(α) has a higher energy than the
spin-down HOMO(β) (ΔE = 2.19 eV). For negatively charged
V(coronene)−, the character of HOMO(α) is similar to that of
neutral HOMO(α). The HOMO(β) is formed by the interaction
between the dxz of the metal atom and the π bond of the coro-
nene molecule. In the case of V2(coronene), its HOMO density
is mostly localized on metal vanadium atoms, mainly consist-
ing of the vanadium dimer sigma σ orbital. The carbon atom
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which was shared by two peripheral rings interacts with the
metal dimer V2. As for the anion V2(coronene)−, the higher
energy HOMO(α) is more favorable for electron removal. The
calculated transition energy 1.73 eV to neutral quintet corres-
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ponds to the detachment of a majority-spin electron from the
HOMO(α). Compared with the neutral V2(coronene), it is
obvious that the HOMO(α) changes from a σ-type (neutral) to a
π-type (anion). For the staggered sandwich V(coronene)2, the
HOMO(α) and HOMO(α) − 2 as well as the HOMO(β) and
HOMO(β) − 1 clearly indicate the bond formation between the
3d orbitals of the V atom and the π electrons of coronene
molecules. Additionally, both HOMO(α) and HOMO(β) have
the same ag symmetry. When an extra electron attaches to
V2(coronene), for HOMO(α), the interaction between the dxz
orbital of vanadium atom and the π orbital of coronene mole-
cules is weaker than that of the neutral complex. In addition,
HOMO(β), HOMO(β) − 1 and HOMO(β) − 2 are similar to that
of neutral V2(coronene), respectively.
We now describe the bond formation between the metal
titanium atom and the coronene molecule. As shown in Fig. 5,
the delocalized π-type orbitals extend over the Ti atom in the
HOMO(α) of Ti(coronene) structure. The HOMO(β) is mostly
made up of metal dxz orbital and the adjacent peripheral ring
π orbital. The π MOs of other rings remain localized around
their rings. For the anionic Ti(coronene)−, its HOMO(α)
obviously corresponds to a σ-type bond with mixed coronene π
characters. For the Ti2(coronene) molecule, the HOMOs are
formed by the interaction of the delta δ orbital of the Ti2 mol-
ecule and the π orbital of coronene. In Ti2(coronene)−, the
HOMO(α) is a π-MO, which is formed by the overlapping of the
out-of-plane of π-MO from the coronene molecule and the dz2
atom orbitals from the two Ti atoms. Meanwhile the two
Ti atoms also bond with each other. Ti(coronene)2 is a closed-
shell system and the formation of 3d–π bonds are also
accomplished in the MOs. The HOMO(α) of Ti(coronene)2−
is dominated by dz2 of the titanium atom, showing weak
Ti–C bonding, while HOMO(α) − 1, HOMO(α) − 2, HOMO(β),
HOMO(β) − 1, and HOMO(β) − 2 present clear 3d–π bond
formation.
3.3 Preferred ring binding
For the coronene molecule, previous work on neutral and cat-
ionic coronene complexes with other metals has discussed
how the peripheral ring seems likely to bind to metal most
effectively. But there is no detailed explanation. It is interesting
to investigate why the peripheral ring is more favorable
towards metal binding.
As is well known, the coronene molecule consists of mul-
tiple benzene rings that are fused together by C–C bonds.
Certain benzene rings contain a different number of C–H
bonds and share a different number of fused C–C bonds with
other rings. Thus, different rings possess different π electron
content and aromaticity. This result may be lead to some rings
being more favorable than others for metal binding. As men-
tioned above, coronene has two types of carbon rings ( periph-
eral and central rings). From the viewpoint of atomic
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Paper
contributions,46 a carbon atom shared by one, two and three
rings contributes 1, 1/2 and 1/3 π electron to each ring,
respectively. The peripheral ring consists of two unshared
carbon atoms, two shared carbon atoms with another ring and
two shared with two other rings. Thus, the π electron content
for the peripheral ring is (2 + 2 × (1/2) + 2 × (1/3))π = 3.67π. For
the central ring, there are six carbon atoms shared by three
rings; thus, the central ring possesses 6 × (1/3)π = 2π electrons.
With respect to the aromaticity, the aromatic index of each
type of carbon ring is defined by the following formula:
αX
HOMA ¼ 1  ðRopt  Ri Þ2 ð1Þ
n
where HOMA is the structure-based harmonic oscillator model
of aromaticity,47 n is the total number of bonds taken into the
summation, and α is an empirical constant for a HOMA = 1
aromatic molecule model with all bonds equal to an optimal
Ropt. For the C–C bonds, α is 257.7, Ropt equal to 1.394 Å, while
the Ri is the bond length from theoretical calculation or experi-
mental measurement. The higher the HOMA value the more
aromatic the ring. For our investigated coronene molecule, the
aromatic index of the peripheral ring was calculated to be 0.74,
which is higher than that of the central ring (0.67). From the
above discussion, we found that the peripheral ring has a
higher π electron content and aromaticity. This enhances the
charge transfer from coronene to the metal atom. Additionally,
we surmise that the peripheral ring sites possess significantly
more electron density which may also be the reason why the
peripheral ring is more likely to bind. So we calculated the
average natural charge populations for the C atoms of the per-
ipheral and central rings in coronene and the (coronene)2 mol-
ecule. the carbon atom in the peripheral ring has a charge
population of −0.124 electrons, while the carbon atom in the
central ring has a charge population of −0.007 electrons. For
the dimer (coronene)2, the average charge populations of the
carbon atoms in the peripheral and central ring are −0.126
and −0.006 electrons, respectively. The comparison of the
charge populations on the peripheral ring and central ring
reveals that there are more electrons residing on the peripheral
ring, which is also more favorable for the charge transfer from
coronene to metal. Thus, the peripheral ring is more favorable
for binding with metal.
3.4 Electronic properties
In section 3.3, the average charge populations for the carbon
atom of the peripheral and central rings in pure coronene and
(coronene)2 have been discussed briefly. Here, in order to gain
deep insight into reliable electronic structure information, the
electron localization function (ELF) was investigated using the
Multiwfn program48 and is sketched in Fig. 6. The structures
of the considered complexes are three-dimensional (3D), so we
plotted the ELF diagrams with 200, 200 grids in two dimen-
sions (2D) defined by three atoms. Additionally, the geometri-
cal structures with the labels of atoms are also presented in
Fig. 6 for a better view. Because the photoelectron spectra of
Ti–coronene complexes are similar to those of the V–coronene
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Fig. 6 Electron localization function plots of pure coronene, (coronene)2 and neutral Vn(coronene)m complexes with different structures together with their geo-
metrical structures and the atom labels.
complexes, and both the anion and neutral V–coronene com-
plexes have a similar structure, we chose the typical neutral
V–coronene complexes (with η6-binding site, η2-bridge site,
sandwich and nonsandwich structures) as examples. The ELF
was originally defined by Axel D. Beck and K. E. Edgecombe in
1990.49 They first argued Dσ as a measure of electron locali-
zation by the following formula:
1 ðrρσ ðrÞÞ2
Dσ ðrÞ ¼ τσ ðrÞ 
4 ρσ ðrÞ
where ρσ is spin electron density, τσ is the positive-definite
kinetic energy. And the electron localization function ELF was
defined as:
ELFðrÞ ¼ ð1 þ χ 2σ ðrÞÞ1
2 5
where χσ(r) = (Dσ(r))/(D0σ(r)) and D0σ ðrÞ ¼ 35 ð6π 2 Þ ρσ ðrÞ. D0σ cor-
3 3
responds to a uniform electron gap with spin density equal to
ρσ. The ratio χσ is a dimensionless localization index calibrated
with respect to the D0σ as reference. Note the value of ELF is
restricted in the range of 0 ≤ ELF ≤ 1. The upper value ELF = 1
corresponds to perfect localization, the ELF = 1/2 corresponds
to electron-gas-like pair probability and the ELF = 0 may corres-
ponds to perfect delocalization (or no electron). Thus, the ELF
not only easily shows atomic shell structure and core, but also
shows bonding and lone pair electrons. It can be clearly seen
from Fig. 6 that there is perfect electron delocalization in these
systems. The ELF map of the monomer coronene clearly shows
that core electrons are localized on carbon and hydrogen
atoms. Lots of covalent bond electrons indicate that the
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covalent component is formed between each two carbon
atoms. Similar observations were found for the (coronene)2
dimer. This indicates that the interaction between the upper
and bottom coronene is very weak and exerts little influence
on their electronic structures. As shown in the 2D map defined
by three atoms (12C, 13C, 37V) of V(coronene), the outside
region around the two C atoms is yellow in appearance. The
bifurcation value of this region is about 0.78, suggesting a sepa-
ration of the core basin. It is interesting to find that some
ð2Þ
electrons are in the form of lone pairs above the V atom. This
phenomenon is also found in V2(coronene) and nonsandwich
V(coronene)2. For the sandwich and nonsandwich V(coro-
nene)2, the vanadium atom has a greater excess electron distri-
bution surrounding it. Additionally, it is worth pointing out
ð3Þ that the V atom in the middle of the two coronene plane may
contribute to the high stability of the sandwich structure.
3.5 Magnetic properties
Magnetism is one of the most prominent properties of tran-
sition metals. Among the transition metal elements, it is well
known that Fe, Co and Ni are ferromagnetic in the standard
bulk phases. It is one of the interesting problems to elucidate
how the magnetic moments of transition metal atoms can be
further affected if these atoms are instead supported on a mole-
cular surface such as benzene (C6H6) and coronene (C24H12).
Earlier studies14 have shown that the magnetic moment of
neutral Sc, Ti and V atoms supported on a benzene molecule
represents a significant increase, Cr atom remain unchanged,
while the neutral Mn, Fe, Co and Ni atoms decrease. Kanda-
lam15 determined that the magnetic moments of Co supported
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Dalton Transactions
Table 5 The spin multiplicity (M) and magnetic moments (μ) for Vn(corone-
ne)m0/− and Tin(coronene)m0/− systems, the magnetic moment unit is μB
System M μ System M μ
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V(coronene) 6 5 Ti(coronene) 3 2
V(coronene)− 5 4 Ti(coronene)− 4 3
V2(coronene) 1 0 Ti2(coronene) 3 2
V2(coronene)− 4 3 Ti2(coronene)− 2 1
V(coronene)2 2 1 Ti(coronene)2 1 0
V(coronene)2− 3 2 Ti(coronene)2− 2 1
on coronene are significantly reduced. Li45 studied Fe–coro-
nene complexes and found that coronene provides the possi-
bility of retaining the high magnetic moment present in the
free Fe atom. For V–coronene and Ti–coronene complexes,
there are very few theoretical studies available on their mag-
netic properties. However, it is very interesting to know how
their magnetic moments would vary relative to that of the cor-
responding free ions. The theoretical calculated dissociation
energies (VEAs and VDEs) match well with the predicted
photoelectron spectra, suggesting that our calculations have
succeeded in determining the features of their electronic
states. One of the important properties of these states is the
spin multiplicity. Because the orbital magnetic moments are
usually very small compared with spin magnetic moments in
metals, the spin magnetic moment is thought to be a reason-
able estimate of the total magnetic moment for a given metal-
containing system. In other words, the spin magnetic moment
is equal to the spin multiplicity minus one. In the present
study, we summarize the spin magnetic moments of these
complexes in Table 5. The ground state of V(coronene),
V(coronene)− and Ti(coronene)− are seen to have a spin mag-
netic moment of 5μB, 4μB and 3μB, respectively. For compari-
son, the spin magnetic moments for a free vanadium and
titanium atom are 3μB and 2μB. The magnetic moments of V
and Ti atoms interacting with the coronene molecule represent
a significant increase. This trend is in agreement with the
earlier reported studies on Ti and V atoms supported on a
benzene molecule.14 While for the neutral Ti(coronene), the
spin magnetic moment remains unchanged, which indicates
that coronene retains the high magnetic moment of atomic Ti.
As for the larger clusters studied here, the spin magnetic
moment of metals V and Ti seems to be reduced compared
with their atomic magnetic moments. This phenomenon can
be interpreted as the solvent coronene molecule acting to
demagnetize the bare metals. Because no experimental results
for these complexes are available, our theoretical findings may
provide a reference for further experimental and theoretical
studies.
4. Conclusions
Neutral and negatively charged Mn(coronene)m (M = V and Ti;
n, m = 1, 2) complexes were studied by DFT theoretical calcu-
lations. By these approaches, we have identified the ground
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state geometries and studied their electronic and magnetic
properties. All the results are summarized as follows:
(1) It was clearly discernible that the metal atom prefers to
occupy the η6-site of the peripheral ring in V(coronene)0/− and
Ti(coronene)− complexes. However, the η2-bridge site of the
perfect structure is definitive on the ground state Ti(coronene).
In M2(coronene), the two metal atoms always form a dimer
and interact with the coronene molecule. Both the sandwich
and nonsandwich structures occur for the M(coronene)20/−
complexes. The sandwich structure of Ti(coronene)20/− com-
plexes is not in agreement with the experiment prediction.25
This should be confirmed by further studies.
(2) The VEA were calculated and compared with the experi-
mental values for the neutral complexes, and the results show
good agreement. Meanwhile, it is interesting to find that the
metal–coronene complexes have significantly greater EA than
the corresponding pure metal atom/dimer and coronene mol-
ecule. Additionally, for some anion complexes, a comparison
of theoretical VDEs with the experimental observation has
allowed us to identify the ground state structure.
(3) By analyzing the pattern of molecular orbitals, we found
that the M–C bond formation mainly consists of the 3d/4s type
of metal atom and π cloud of coronene. Then, we systemati-
cally explained the reason why the peripheral ring site binds
metal most effectively by analyzing the π electron content, aro-
maticity and average charge on the carbon atoms. ELF for the
considered complexes show that there is perfect electron delo-
calization in these systems.
(4) The magnetism of Mn(coronene)m (M = V and Ti; n, m =
1, 2) complexes was investigated. The spin magnetic moment
of V and Ti atom in V(coronene)0/− and Ti(coronene)− rep-
resents a significant increase compared with their atomic mag-
netic moments. This trend is in agreement with the earlier
reported studies14 on Ti and V supported on one benzene mol-
ecule. While the spin magnetic moment remains unchanged
in neutral Ti(coronene). In the larger complexes studied here,
it appears to be reduced.
Acknowledgements
The authors are grateful to the National Natural Science Foun-
dation of China (No. 10974138 and No. 11104190) and the
Doctoral Education Fund of Education Ministry of China
(No. 20100181110086 and No. 20111223070653).
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