Article

pubs.acs.org/JPCA

Compositions and Structures of Vanadium Oxide Cluster Ions VmOn±

(m = 2−20) Investigated by Ion Mobility Mass Spectrometry
Jenna W. J. Wu,† Ryoichi Moriyama,† Hiroshi Tahara,† Keijiro Ohshimo,†,‡ and Fuminori Misaizu*,†
†
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai 980-8578, Japan
‡
Institute for Excellence in Higher Education, Tohoku University, 41 Kawauchi, Aoba-ku, Sendai 980-8576, Japan
*
S Supporting Information

ABSTRACT: Stable compositions and geometrical structures of vanadium oxide cluster

ions, VmOn±, were investigated by ion mobility mass spectrometry (IM-MS). The most stable
compositions of vanadium oxide cluster cations were (V2O4)(V2O5)(m−2)/2+ and (VO2)-
(V2O5)(m−1)/2+, depending on the clusters with even and odd numbers of vanadium atoms.
Compositions one-oxygen richer than the cations, such as (V2O5)m/2− and (VO3)-
(V2O5)(m−1)/2−, were predominantly observed for cluster anions. Assignments of these stable
cluster ion compositions, which were determined as a result of collision-induced dissociations
in IM-MS, can partly be explained with consideration of spin density distribution. By
comparing the experimental collision cross sections (CCSs) obtained from ion mobility
measurement with CCSs of the theoretically calculated structures, we confirmed the
patterned growth of geometrical structures partially discussed in previous theoretical and
spectroscopic studies. We showed that even sized (V2O5)m/2± where m = 6−12 had right
polygonal prism structures except for the anionic V12O30−, and for the clusters of odd numbers of vanadium m, cations and
anions can either have bridged or pyramid structures. Both of the odd sized structures proposed were derivatives from the even
sized right polygonal prism structures. The exception, V12O30−, which had a CCS almost equal to that of the neighboring smaller
V11O28−, should have a structure of higher density than the right hexagonal prism, in which it was proposed to be a captured
pyramid structure, derived from V11O28−.

1. INTRODUCTION anionic,9,14−16 and neutral11,12,17 species. The structures of

A vanadium atom can take various oxidation states within the
range of +2 to +5. Bulk phase vanadium oxides exist in various
chemical compositions with different oxidation states, such as
VO with V (+II), and V2O5 with V (+V). Among these
compositions, bulk V2O5 is found to be the most stable because
the vanadium atoms are fully oxidized in the bulk solid crystals.
Bulk V2O5 is also well-known as an oxidation catalyst, which is
used widely in industries. Some examples of its industrial usage
are catalytic oxidation of SO2 to SO3 in the synthesis of sulfuric
acid1 and selective oxidation of hydrocarbon molecules.2 In
other applications, bulk vanadium oxide is studied as cathode
materials of lithium batteries or as thin-film materials in optical
switching devices.3
Gas-phase vanadium oxide clusters (VmOn) were studied
experimentally and were often complemented by theoretical
studies to achieve a better understanding of their reactivity and
their roles in catalysis. Experimentally, mass spectrometry was
applied to studies not only on cationic4−8 and anionic9 clusters,
but also on neutral10−12 vanadium oxide clusters. The collision-
induced dissociation studies by Castleman and co-workers on
the small vanadium oxide clusters ions of m = 2−7 indicated
that VO2, VO3, and V2O5 were the main building blocks for
both cationic6 and anionic9 species.
To understand the formation process and structures of
vanadium oxide clusters, theoretical studies on structures based
on V2O5 units were also examined for small cationic,5,6,13
cationic clusters were suggested by Duncan and co-workers for
group 5 metal oxides (MnOm; n = 1−5; M = V, Nb, and Ta).5
Bernstein and co-workers worked on small, neutral vanadium
oxide clusters with density functional theory.11,12 For neutral
vanadium oxide clusters having an even number of vanadium
atoms, which are expressed by (V2O5)x up to x = 12, right
“polygonal” prism and polyhedral structures were suggested by
quantum chemical calculations by Vyboishchikov and Sauer.17
The structures of the anionic vanadium oxide clusters with an
odd number of vanadium atoms, expressed as (VO3)-
(V2O5)1−3−, were suggested by infrared multiphoton dissocia-
tion spectroscopy and calculations.14 In this work, Asmis and
co-workers obtained the vibrational spectra of structural
isomers such as pyramid structure and bridged structures of
V5O13−, which had an extra top of vanadium atom on the even
sized polygonal prism structures. Structures of neutral, cationic,
anionic (V2O5)1−3, and anionic (VO3)(V2O5)1−2− are shown in
Figure 1 as examples of stable structures from past studies. The
study of small gas-phase vanadium oxide cluster anions by
Wang and co-workers based on anion photoelectron spectros-
copy also gave insights into the electronic structures of the
cluster anions and into V−O chemical bonding properties.18,19
Received: April 4, 2016
Revised: May 9, 2016

© XXXX American Chemical Society A DOI: 10.1021/acs.jpca.6b03403

J. Phys. Chem. A XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry A
Figure 1. Structures of neutral, cationic, and anionic even sized
clusters V2O5, V4O10, V6O15 and anionic odd sized clusters V3O8− and
V5O13− calculated in previous studies.13,14,17 Red spheres are vanadium
atoms, and blue spheres are oxygen atoms. The basic framework
structures are shown in the figure, and vanadium oxide clusters are
formed by placing vanadium atoms on the vertices of these
polyhedrons.
In addition, experiments based on reactivity of vanadium oxide
cluster ions were also studied as models of catalytic oxidation
reaction on the bulk crystals, such as the reaction with SO2,20
H2O,21 and some organic molecules.22−24
Ion mobility mass spectrometry (IM-MS), which is a
combination of both ion mobility spectrometry (IMS) and
mass spectrometry (MS), is a powerful method to elucidate the
geometrical structures of gas-phase cluster ions.25−27 Structural
information on cluster ions is obtained as collision cross
sections (CCSs), which can be evaluated by measuring the
mobility of ions inside a buffer-gas-filled ion drift cell of IMS.
Although it is difficult to determine detailed structural
parameters of each cluster ion directly from CCSs, IM-MS is
easily applicable for larger sized cluster ions by a combination
with quantum chemical calculations.
In this study, the most abundant compositions of vanadium
oxide cluster cations and anions (VmOn±, m ≤ 20) were first
determined by mass spectra from IM-MS, in which collision-
induced dissociation of the cluster ions occurred. Specific
geometrical structures of these compositions with growing
patterns partially discussed by previous studies5,11,12,14,17 were
calculated by quantum chemical calculations. Finally, the
structures were assigned by comparison of theoretical CCSs
derived from calculated structures with experimental CCSs
measured by IM-MS.
2. EXPERIMENTAL AND COMPUTATIONAL METHODS
IM-MS experiments were performed using a home-built
vacuum apparatus composed of a cluster ion source, an ion
drift cell, and a reflectron time-of-flight (TOF) mass
spectrometer. Details of this experimental setup and procedures
for IM-MS were reported elsewhere.28−31 Vanadium oxide
cluster ions, VmOn±, were generated by a combination of laser
vaporization of a vanadium rod and supersonic expansion of a
5% O2/He gas mixture. Stagnation pressure of the O2/He
mixture gas was 3 atm. Vaporized vanadium atoms/ions and O2
molecules collide with one another and grow to large vanadium
oxide cluster ions in the region immediately after the
vaporization laser irradiation point. The generated cluster
ions were injected into the ion drift cell with a kinetic energy
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(injection energy, Einj) of 50−250 eV by a pulsed electric field.
The 100 mm long ion drift cell with an applied 10 V/cm
electric field was filled with 0.80 Torr of helium buffer gas, and
it was further cooled to 190 K with liquid nitrogen. When
cluster ions were injected into the cell especially with high Einj,
ions had collision-induced dissociations by the collisions with
the He atoms at the inlet of the cell as noted below. Finally,
product ions from these reactions passed through the cell. In
our previous study for sodium fluoride cluster cations, stable
magic number cluster cations were clearly observed as collision-
induced dissociation products under high Einj conditions.32
The velocity of the cluster ions injected into the cell was
decreased by collisions with He buffer gas atoms at the inlet of
the cell. However, because of a balance between deceleration by
buffer gas collisions and acceleration by the applied electric
field, E, inside the cell, drift velocity of the ions, vd, becomes a
constant value that is proportional to E, that is
vd = KE (1)
in which the coefficient K is known as ion mobility.23 An
equation of the ion mobility K of thermalized ions drifting
through the buffer gas with an applied electric field was given
from the kinetic theory33 as
3e ⎛ 2π ⎞
1/2
1
K= ⎜ ⎟
16N ⎝ kBμTeff ⎠ (1,1)
Ω (2)
where e is the elementary charge, N the number density of the
buffer gas, kB the Boltzmann constant, μ the reduced mass of
the ion and the buffer gas atom, and Ω(1,1) a collision integral
representing an average of momentum transfer cross section
over collision energy and orientations. When we treat the ion
and the neutral as hard sphere without internal states, the
collision integral is reduced to the hard-sphere CCS, Ω. The
term Teff, effective temperature of the ions, is given by TBG +
mBvd2/3kB, where TBG is the buffer gas temperature and mB is
the mass of a buffer gas atom.
After exiting the ion drift cell, the ions were reaccelerated by
another pulsed electric field in an acceleration region of the
TOF mass spectrometer. We denote the time difference, Δt,
between ion injection pulse and reacceleration pulse as “arrival
time”. An effective time, teff, that ions spent in the cell was
derived from subtracting the time that ions flew outside of the
cell, tex, from the arrival time, Δt, i.e., teff = Δt − tex. The drift
velocity, vd, is easily calculated by dividing the length of the ion
drift cell (100 mm) by teff. Therefore, we can estimate the ion
mobilities and CCSs of the cluster ions by measuring the arrival
time for each cluster ion with eqs 1 and 2.28−32 In the IM-MS
measurement, we obtained a series of TOF mass spectra
sequentially by scanning the arrival time automatically with
LabVIEW program. Then, these data were summarized in a
two-dimensional (2D) plot of mass number versus arrival time.
In IMS, the ratio of the drift electric field, E, to the number
density of buffer gas, N, is an important parameter. Typically, in
other IMS experiments, the E/N values were 1.5−10 Td (1 Td
= 10−17 V cm2).33,34 It is desirable to keep E/N low for
measuring the precise CCSs of ions in the low field limit (E/N
→ 0 Td) because the mobility of ions in high E/N conditions
deviates from the data in the low field. On the other hand, the
amount of the cluster ions after the separation decreases at low
E/N conditions because of scattering by many collisions with
buffer gas. Therefore, we searched for the highest possible E/N
conditions for determining the structures of cluster ions. In the
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Figure 2. Mass spectra of vanadium oxide cluster cations and anions with injection energies of (a) cations in 50 eV, (b) anions in 50 eV, (c) cations
in 250 eV, and (d) anions in 250 eV condition. Compositions of some corresponding stable species are as labeled.
present experiments, conditions were optimized with E/N = 24
Td when buffer gas pressure and temperature in the ion drift
cell were 0.80 Torr and 190 K, respectively.
The structures of vanadium oxide cluster ions, VmOn±, were
calculated for 2 ≤ m ≤ 12 by B3LYP/6-311+G(d) level of
theory with Gaussian 09.35 Theoretical CCSs of the cluster ions
were calculated from these ionic structures by using the
projection approximation method,36 which is included in
MOBCAL program.37 In this approximation, we assumed that
the orientationally averaged projected area is exactly equal to
the CCS. The projection approximation method requires the
hard sphere atomic radii of each atom in a molecule and does
not require the charge distributions of a molecule. The hard
sphere radii of vanadium and oxygen atoms in the cluster
cations and anions were determined so that theoretical CCSs of
V8O20± reproduce experimental CCSs of V8O20+ cation and
V8O20− anion, where the experimental CCSs were 122 ± 5 and
123 ± 5 Å2, respectively. The radius ratio of vanadium and
oxygen atoms was fixed to account for the radius relation of
crystal vanadium oxide (V5+: O2− = 0.495:1.21).38 The resulting
hard sphere radii for cations and anions coincided to be V (0.62
Å) and O (1.51 Å). In addition, a radius of 1.15 Å for neutral
He atom, the buffer gas atom, was used in the calculation.36
The fitted theoretical CCSs of V8O20± were 122 and 123 Å2,
respectively, under projection approximation (PA). The
theoretical CCSs of tetrahedral structured V4O10± were
therefore estimated to be 78 and 79 Å2. As a reference, the
CCSs of V8O20± were both 133 Å2, and those of V4O10± were
both 82 Å2 under the exact hard sphere approximation (EHSS),
which is another evaluation method of CCSs in MOBCAL.
When the hard-sphere contact distance is the same as that of
PA, it was reported that the CCSs by EHSS are in general
overestimated compared to those by PA.39 Because we found
that these differences between PA and EHSS do not affect the
results and discussion in the present study, simple PA was
adopted for calculating CCSs throughout this study.
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3. RESULTS AND DISCUSSION
3.1. Compositions and Arrival Time Distributions of
Vanadium Oxide Cluster Ions. 3.1.1. Composition Assign-
ment. Mass spectra of vanadium oxide cluster cations and
anions (VmOn±), obtained by IM-MS measurement, both in
injection energy of 50 and 250 eV conditions, are shown in
Figure 2. These mass spectra of the gas-phase cluster ions were
obtained by summing all the ion signals exiting the ion drift cell
with spatial distributions depending on their mobilities.
Panels a and b of Figure 2 show the mass spectra for both
vanadium oxide cluster cations and anions, respectively,
observed in low injection energy condition (Einj = 50 eV)
with the range from 0 to 2000 mass number. From these mass
spectra, multiple species of different number of oxygen atom n
can be observed for each vanadium atom number m. For
example, when m = 5, V5O11−14+ were observed in Figure 2a for
cluster cations and V5O12−14− were observed in Figure 2b for
cluster anions.
On the other hand, Figure 2c,d shows the mass spectra of
both cations and anions observed under high Einj condition
(250 eV). Compared with the lower injection energy condition,
the number of species with different oxygen number n in each
m series decreases in Figure 2c,d. For the same example as
above, when m = 5, V5O11−13+ and V5O12−13− were observed.
Also, the ion signals in Figure 2c,d of cluster sizes m ≤ 5 are
relatively higher than cluster sizes m > 5. In this injection
energy condition, collision-induced dissociation was more likely
to occur at the inlet of the ion drift cell and larger clusters were
dissociated into more stable smaller clusters or into stable
compositions. Cluster ions that cannot be further dissociated
are considered stable and abundantly observed in this
condition. The most abundant species found in the 250 eV
condition can also be observed in the 50 eV condition;
however, some of them were not the major species at the 50 eV
condition. For m = 5, V5O12+ was mainly observed at 250 eV,
while ion signal of V5O13+ was more intense than V5O12+ at the
50 eV condition.
From the mass spectra in Figure 2c,d, the stable
compositions can be assigned as the most abundantly observed
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compositions. We realized that all vanadium oxide cluster ions
have compositions containing the V2O5 unit depending on
whether the number of the vanadium atom is even or odd. For
even sized cations, (V2O4)(V2O5)(m−2)/2+ was the most
prominent composition, whereas (V2O5)m/2+ was the second
or third most prominent composition in this condition. For
even sized anions, the composition of (V2O5)m/2− was the most
abundant and (V2O4)(V2O5)(m−2)/2− was the second most
abundant. For example, V10O24+ was the most prominent and
V10O25+ was the third most prominent for cations. On the other
hand, V10O25− was the most prominent and V10O24− was the
second most prominent for anions. With odd sized clusters,
compositions of (VO2)(V2O5)(m−1)/2+ for cations and (VO3)-
(V2O5)(m−1)/2− for anions were the most prominent. As
examples of odd sized ions, V5O12+ and V5O13− were
predominant for cations and anions, respectively. The
composition found here for vanadium oxide cluster cations
was consistent with the abundant species found by Kurokawa
and Mafuné for cluster sizes m = 2−10.8 Also, in previous
photodissociation experiments4,5,14 and a collision-induced
dissociation experiment,6 the compositions observed in this
study were commonly produced as fragments from various
parent ions (m < 10). The commonly produced fragments are
VO2+, V2O4+, V3O7+, V4O9+, V5O12+, and V6O15+ or VO3−,
V2O5−, V3O8−, V4O10−, V5O13−, and V6O15−, along with other
ions with different number of oxygen atoms. The present
results of the most abundantly observed compositions were also
consistent with the observations made by Castleman et al. The
observation was that anions tend to have a one-oxygen richer
composition than the cations,6,9 and in addition, we are able to
extend this observation to cluster sizes up to m = 20.
Using the impulsive collision theory40 under multiple
collisions (see Supporting Information), the total averaged
internal energy transferred to the cluster ions from 250 eV
relative kinetic energy collisions with He buffer gas was
estimated. The estimated energy was 33 eV on average for
cluster sizes larger than V4O10±. This internal excitation energy
can be partitioned to internal degrees of freedom, and finally it
can exceed bond dissociation energy of the cluster ion. After
the cluster ions lose their kinetic energies by the collisions and
reach constant drift velocities, they rarely dissociate by the
collisions with light He buffer gas inside the cell. In the mass
spectra, signals of the resultant ions were observed after such
dissociations. Therefore, they were assigned as stable
compositions with respect to collision-induced dissociations
for vanadium oxide cluster cations and anions.
On the other hand, total averaged energy transferred to the
cluster ions from the initial relative kinetic energy at Einj = 50
eV was estimated to be 6.5 eV for ions larger than V4O10± by
the impulsive collision theory noted above. Moreover, center-
of-mass collision energy of one collision, which is defined by
the product of the reduced mass of the collision pairs (a
vanadium oxide cluster ion and a He atom) and the relative
velocity,41 was estimated to be smaller than 1 eV for each
collision under 50 eV injection energy condition with ions
larger than V4O10±. By comparison, Castleman and co-workers
reported collision-induced dissociation of vanadium oxide
cluster ions with xenon gas with the center-of-mass collision
energy of 3−5 eV.6 Though energy of a single collision is
smaller in the present experiment, dissociation is possible
because the clusters undergo multiple events of collisions at the
inlet of the ion drift cell. Therefore, dissociation could still
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occur in this low Einj condition, but the possibility of the
dissociation should be much less than in the high Einj condition.
Additionally, by observing the peak intensity of each
vanadium atom number series m from the mass spectra in
Figure 2, it was clear that cluster ions having an odd number of
vanadium atoms were generally more stable than those with an
even number of vanadium atoms. The stability of odd sized
clusters, (VO2)(V2O5)(m−1)/2+ and (VO3)(V2O5)(m−1)/2−, could
be explained by the electron shell closing of the clusters. The
ionized form of these clusters are of closed-shell stoichiometry,
in which all of the vanadium atoms take the most stable and
common +V oxidation state, and oxygen atoms of −II oxidation
state. The stability of some small (m = 1−7) cationic6 and
anionic14 compositions were also discussed in past studies. In
contrast to the closed-shell odd sized cluster ions, cluster ions
with an even number of vanadium atoms such as (V2O4)-
(V2O5)(m−2)/2± and (V2O5)m/2± contained vanadium atoms of
two different oxidation states, +IV and +V. Uneven number of
electrons in the even sized cluster ions form open-shell species.
The fact that all odd sized ions were closed shell, which is also
electronically stable, and even sized ions are open-shell species
should be one of the reasons why the intensities of all odd sized
ions were almost always higher than those of neighboring even
sized ions in the mass spectra. The odd size series stability is
clearly visible for the first time in the present mass spectra by
the use of IM-MS, in which cluster ions can be successfully
separated and had collision-induced dissociation before mass
analysis.
As noted above, the even sized (V2O5)m/2± clusters were the
second or third most prominent for cations and the most
prominent for anions in the mass spectra. This composition
corresponds to the polyhedron and polygonal prism structures
in Figure 1, as calculated in previous studies.14,17 However, one-
oxygen deficient compositions, (V2O4)(V2O5)(m−2)/2+, were the
predominant composition for even sized cations. This differ-
ence of the primary compositions in cations and anions could
be explained by the difference on the distributions of a lone pair
of electrons. It was reported by Schwarz and co-workers that for
the small polyhedral (V2O5)m/2+ cations such as V4O10+, spin
density distribution was localized at one of the bonds between a
terminal oxygen and a vanadium atom.42 Figure 3a shows the
spin density distribution around the terminal oxygen of the
tetrahedral structured V4O10+, which was also calculated in this
study. Spin density distributions of V6O15+ and V8O20+ are also
Figure 3. (a) Calculated spin density distribution of V4O10+, V6O15+,
and V8O20+. The distribution was localized around one terminal
oxygen atom. (b) Calculated spin density distribution of V4O10−,
V6O15−, and V8O20−, which was delocalized around vanadium atoms.
J. Phys. Chem. A XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry A
shown in Figure 3a assuming their structure to be triangular
prism and square prism, which will be discussed in a later
section. The spin density distributions are probably localized on
the antibonding orbitals between the terminal oxygen atom and
the vanadium atom; therefore, they cause extension of the
corresponding bonds. When the spin density localization
property is extrapolated, this extended and destabilized V−O
bond in (V2O5)m/2+ cations could dissociate easily by collisions
with He buffer gas in high Einj conditions at the inlet of the cell
in our experiment. Therefore, (V2O4)(V2O5)(m−2)/2+, the one-
oxygen deficient species, became the most prominent for
cations as a result of the dissociation of terminal oxygen. On the
other hand, for the anions, spin density distribution was
delocalized around d orbitals of all vanadium atoms in V4O10−,
and a vanadium atom in V6O15− or V8O20−, which was
discussed by Asmis and co-workers,15 as shown in Figure 3b.
Thus, the extra electron in the anion is not localized on the
antibonding orbital, which causes extension of the correspond-
ing bond length. As a result, it is suggested that (V2O5)m/2− was
less likely to dissociate into (V2O4)(V2O5)(m−2)/2− rather than
the cationic species (V2O5)m/2+.
3.1.2. Collision Cross Section Analysis with ATD. The
analysis and discussion were focused on the compositions
(V2O5)m/2± for cluster ions having an even number of vanadium
atoms and (VO2)(V2O5)(m−1)/2+ and (VO3)(V2O5)(m−1)/2− for
those having odd number of vanadium atoms, because these
were predominant species found in mass spectra measured in
the high injection energy condition. However, to estimate
accurate experimental CCSs, arrival time distributions (ATDs)
of each ion should be measured under the low injection energy
condition (Einj = 50 eV). The high Einj condition not only
causes collision-induced dissociation resulting in stable species
but also causes a longer deceleration time for the cluster ion
until the ion reaches a constant drift velocity (vd). As a result,
the injected ions tend to have shorter arrival times; thus, the
high Einj condition finally results in an underestimation of
CCSs. At the low Einj condition, cluster ions with various
oxygen atoms were observed rather than the high Einj condition
(such as V5O13+ is observed in 50 eV spectrum in Figure 2), yet
the desired (in this case, V5O12+) for analysis were still
observable.
Figure 4 shows typical ATDs obtained under the Einj = 50 eV
condition for vanadium oxide cluster cations and anions with
the range between m = 2−20. The designated cluster
compositions are (V 2 O 5 ) m/2 + (m; even) and (VO 2 )-
(V2O5)(m−1)/2+ (m; odd) for cations, along with (V2O5)m/2−
(m; even) and (VO3)(V2O5)(m−1)/2− (m; odd) for anions. Red
solid curves in the ATD plots are Gaussian functions used to fit
the experimental plots and to obtain the representative arrival
times as the center positions of the distributions. These ATDs
were constructed from the 2D plots of arrival time versus mass
of these ions shown in Figure S2 by scanning the mass of
cluster ions at specific arrival times.
The ATDs of vanadium oxide cluster cations shifted to a
longer time monotonically with increasing m from 2 to 20,
along with a gradual increase of bandwidth of ATDs, as shown
in Figure 4. Similarly, the ATDs of the anions shifted to a
longer arrival time from m = 2−11. However, different from the
cations, a stepwise growth of ATD was observed for the cluster
anions with sizes around m = 12−18. For example, arrival time
of the even sized (V2O5)m/2− ion at m = 12, V12O30−, almost
coincided with that of the neighboring odd sized (VO3)-
(V2O5)(m−1)/2−, m = 11, V11O28−. Furthermore, the broad
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Figure 4. Arrival time distributions of vanadium oxide cluster cations
(left panel) and anions (right panel) in the range m = 2−20, obtained
with injection energy of 50 eV. The red curves are Gaussian functions
that fit the experimental values shown as white circles.
ATDs of odd sized anion m = 13, 15, 17 and 19, can be fitted
with two Gaussian functions rather than those of neighboring
even sized anions. This result indicates the possibility that a
signal originating from multiple structural isomers was included
in these ATDs.
3.2. Prediction of the Cluster Structures by Quantum
Chemical Calculation. To reveal the structures of the
observed cluster ions in IM-MS, optimized structures of the
cluster ions, VmOn±, for the compositions noted in section 3.1.2
were calculated by quantum chemical calculations with B3LYP/
6-311+G(d) level up to m = 12. As for the structures obtained
with the present calculation level, the geometries and the bond
lengths of the ions agreed well with other calculations reported
previously.42,43 For example, bond lengths between the
vanadium atom and terminal oxygen in the tetrahedral
V4O10± are 1.55 Å for cations and 1.59 Å for anions, whereas
1.72 Å was found for cations42 and 1.81 Å for anions.43 Because
the stable composition of vanadium oxide cluster cations and
anions had an even and odd size dependency, the structures
should also be considered based on such composition
dependency. As briefly discussed in the Introduction, neutral,
cationic, and anionic (V2O5)x 0/± (x = 2, 3, 4) species were
proposed to be tetrahedral and right polygonal prism
structures,15 and odd sized (VO3)(V2O5)1−3− anionic species
were pyramid and bridged structures.14,15 In addition to these
structures discussed in past studies, we will propose in this
study some new cluster ion structures based on their parity
dependency and also suggest a patterned structural growth with
increasing cluster size.
First, the even sized (V2O5)m/2±, structures for m = 6−12 as
patterned right polygonal prism structures and polyhedron
structures for m = 4 and 12 are shown in Figure 5, in which
both structures for m = 12 are newly proposed in this study. All
of the vanadium atoms configure the framework structures as
vertices of the polyhedrons (V4O10± and V12O30±) and the right
polygonal prism structures [(V2O5)m/2±, m = 6, 8, 10, 12]. It is
found that 60% of the oxygen atoms locate on every edge of the
framework structures forming V−O−V bonds, and the
remaining 40% oxygen atoms bond to vanadium atoms on
the vertices as terminal oxygen. This oxygen percentage applies
for all of the right polygonal prism structures and the
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Figure 5. Optimized structural candidates of the clusters with even number of V atoms (left panel) and those with odd number of V atoms (middle
and right panels) calculated with B3LYP/6-311+G(d). Relative energies are indicated for the two isomeric structures.

polyhedron structures in Figure 5. The even sized clusters grow

with an increment of V2O5 in the polygonal prism structure
with an expansion of the polygon, from triangle, to tetragon
(square), to pentagon, and then to hexagon.
Next, two structural candidate patterns of the odd sized
cluster ions were predicted for both (VO2)(V2O5)(m−1)/2+ and
(VO3)(V2O5)(m−1)/2− as shown in Figure 5. These structural
candidates of each odd sized composition were derived from
the neighboring even sized ions by an addition of VO2 or VO3.
For the first structural candidate, an extra VO2 or VO3 was
added to one edge of the triangle in the triangular prism of
V6O15± to form the bridged structure of V7O17+ or V7O18−. For
the second type of structural candidate, pyramid structure of
V7O17+ or V7O18−, an extra VO2 or VO3 was added to one face
of the triangular prism V6O15±, and the extra oxygen in the
anions became terminal oxygen on the top of the five
coordinated vanadium atom. Following these patterns, new
structures for bridged and pyramid structures were proposed
for odd sized ions of m = 9 and 11.
Figure 6. Experimental collision cross sections (blue marks, Ωexp.) and
3.3. Structure Assignments by Comparisons between theoretical collision cross sections (colored marks, Ωcalc.) for both
Experimental and Theoretical Results. Experimental and cluster (a) cations and (b) anions. The experimental collision cross
theoretical CCSs of cationic and anionic clusters are shown in sections of m = 2−20 were measured in 50 eV injection energy
Figure 6 and Tables 1 and 2. All experimental data were condition. The calculated cross sections are indicated for m = 2−12.
measured under the low injection energy condition (50 eV).
Experimental CCSs of even sized (V2O5)m/2+ and odd sized
(VO2)(V2O5)(m−1)/2+ were plotted in Figure 6a for m = 2−20. can reproduce the experimental CCSs of cation (122 ± 5 Å2)
Similarly, experimental CCSs of even sized (V2O5)m/2− and odd and anion (123 ± 4 Å2). As for cations, the theoretical CCSs of
sized (VO3)(V2O5)(m−1)/2− were plotted in Figure 6b. The the right polygonal prism structure pattern had good agreement
errors of experimental CCSs were estimated from standard with experimental CCSs of even sized clusters, (V2O5)m/2+, for
deviations of the data obtained by three (cations) and six the sizes m = 6−12 as shown in Figure 6a. Trigonal prism
(anions) independent measurements. All of the theoretical structure of V6O15+ had an experimental CCS of 104 ± 5 Å2
CCSs of the proposed structures in Figure 5 were also plotted and a theoretical CCS of 102 Å2 right within the standard
in Figure 6. deviation. Likewise, the prism structures of V10O25+ and
As noted in section 2, in the calculations of CCSs by the V12O30+ had good matches in CCSs with experimental values:
projection approximation method in MOBCAL, the hard 142 Å2 to 142 ± 7 Å2 and 162 Å2 to 161 ± 8 Å2, respectively.
sphere radii of V and O atom were determined so that The polyhedron structure of V12O30+, which had the same CCS
theoretical CCSs of right tetragonal prism (cubic) of V8O20± as the right hexagonal prism structure (162 Å2), was more
F DOI: 10.1021/acs.jpca.6b03403
J. Phys. Chem. A XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry A Article

Table 1. Experimental CCSs (Ωexp) and Theoretical CCSs V7O17+ are clearly broader than those of V2O5+, V4O10+, and
(Ωcalc) Calculated by MOBCAL of Vanadium Oxide Cluster V6O15+. This feature is most likely due to the coexistence of
Cations isomers. However, it is not possible to explain the origin of the
broad ATDs with only the two isomers shown in Figure 5
Ωcalc (Å2)
because experimental CCSs are always slightly larger than both
cation Ωexp (Å2) linear prism bridged pyramid polyhedron of them, as shown in Table 1. Not only these isomers but also
+
V2O5 63 54 other structures which are not discussed here may coexist in
V3O7+ 73 ± 3 68 V3O7+, V5O12+, and V7O17+.
V4O10+ 81 ± 3 78 For the anions, the right polygonal prism structure pattern
V5O12+ 93 ± 5 88 85 agreed well with experimental values up to m = 10 for even
V6O15+ 104 ± 5 102 sized vanadium oxide cluster anions, (V2O5)m/2− as shown in
V7O17+ 113 ± 8 110 105 Figure 6b. The theoretical CCSs of V6O15− was 102 Å2 in
V8O20+ 122 ± 5 122 comparison with experimental CCS 102 ± 3 Å2, and similarly,
V9O22+ 131 ± 11 129 127 V10O25− was 142 Å2 in comparison to experimental CCS 140 ±
V10O25+ 141 ± 7 142 4 Å2. As described in section 3.1.2, V12O30− had a smaller arrival
V11O27+ 151 ± 8 150 146 time close to that of V11O28−, 151 ± 5 Å2. Therefore, the
V12O30+ 161 ± 8 162 162 structure of V12O30− should be more compact than the right
V13O32+ 166 ± 7 hexagonal prism structure or the polyhedron structure both
V14O35+ 176 ± 7 with theoretical CCSs of 162 Å2, which will be considered in
V15O37+ 183 ± 8 the next paragraph. On the other hand, for the odd sized
V16O40+ 193 ± 8 anionic clusters, bridged structures are slightly more stable in
V17O42+ 198 ± 9 energy of approximately less than 0.2 eV than pyramid
V18O45+ 208 ± 9 structures for m = 5, 9, and 11. However, the pyramid
V19O47+ 213 ± 9 structure of m = 7 is 0.22 eV more stable than the bridged
V20O50+ 221 ± 9 structure. When the experimental and theoretical CCSs are
compared, the more compact pyramid structures had better
energetically stable and an equally possible structure (not agreement with experimental values. Because the two types of
plotted in Figure 6a). For the two structural candidates of odd structures had relatively close energy, the pyramid structure
sized vanadium oxide cluster ions, (VO2)(V2O5)(m−1)/2+, pattern can be assigned to the odd sized (VO3)(V2O5)(m−1)/2−
bridged structures were 2−4 Å2 larger in CCSs in comparison (m = 5, 7, 9, and 11) for their better match in experimental
with the pyramid structures. The bridged structures were also CCSs.
more stable energetically by approximately 1.6−0.5 eV than the The experimental CCS of V12O30−, 151 ± 5 Å2, was relatively
pyramid, as shown in Figure 5. Thus, even though both of the close to the experimental CCS of the neighboring smaller odd
structural candidates had theoretical values well within the size species V11O28− (150 ± 5 Å2); therefore, they should have
standard deviation of the odd sized cluster ions, the bridged structures of similar theoretical CCSs. A structure derived from
structure pattern can be assigned to V5O12+, V7O17+, V9O22+, V11O28− pyramid structure was proposed as shown in Figure 7.
and V11O27+. In addition, the ATDs of V3O7+, V5O12+, and An additional VO2 was added to the cavity within the pyramidal

Table 2. Experimental CCSs (Ωexp) and Theoretical CCSs (Ωcalc), Calculated by MOBCAL, of Vanadium Oxide Cluster Anionsa
Ωcalc (Å2)
anion Ωexp (Å )
2
linear prism bridged pyramid polyhedron
V2O5− 61 56
V3O8− 71 ± 4 70
V4O10− 79 ± 3 79
V5O13− 93 ± 3 94 90
V6O15− 102 ± 3 102
V7O18− 113 ± 3 117 112
V8O20− 123 ± 4 123
V9O23− 131 ± 3 136 132
V10O25− 140 ± 4 142
V11O28− 150 ± 5 155 152
V12O30− 151 ± 5 162 162
V13O33− 149 ± 6 165 ± 6
V14O35− 162 ± 5
V15O38− 170 ± 4 183 ± 5
V16O40− 175 ± 6
V17O43− 182 ± 6 196 ± 7
V18O45− 189 ± 5
V19O48− 195 ± 6 208 ± 6
V20O50− 202 ± 8

a
The experimental CCSs of structural isomers are also included.

G DOI: 10.1021/acs.jpca.6b03403
J. Phys. Chem. A XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry A
Figure 7. Additional structural candidate of V12O30− derived from the
pyramid structure of V11O28− by an addition of VO2 into the cavity
inside the pyramid, optimized by B3LYP/6-311+G(d). The
corresponding theoretical collision cross sections (Ωcalc.) calculated
by MOBCAL are also shown as labeled.
structure of V11O28− to form V12O30−, and it was optimized
with B3LYP/6-311+G(d). The structural optimization sug-
gested that this “pyramid capture” structure was relatively more
compact (153 Å2) than the right hexagonal prism and the
polyhedron structures (162 Å2) and was similar to the pyramid
structure of V11O28− (152 Å2). Even though this pyramid
capture structure provided a better theoretical-to-experimental
value comparison, we cannot ignore the fact that this structure
was about 1.28 eV less stable than the hexagonal prism and 1.43
eV less stable than the high-symmetry polyhedron structure.
Species like V12O30− were necessary to have structures with
higher density; thus, it can possibly include a VO2 inside the
structural cavity of the odd sized species to decrease the overall
CCS, as described in Figure 7.
Meanwhile, by observing the experimental CCS growth of
the cluster anions carefully in Figure 6b and Table 2, we can see
that the bulkier isomer for sizes m = 13, 15, 17, and 19 may be
an extension of odd sized cluster ion growth similar to those of
cluster cations. In fact, the larger isomer for sizes m = 13, 15,
17, and 19 had experimental CCSs similar to those of cluster
cations with the same number of vanadium atoms. For example,
the cationic V13O32+ had an experimental CCS of 166 ± 7 Å2,
and the anionic V13O33− was 165 ± 6 Å2; moreover, V15O37+
was 183 ± 8 Å2, whereas V15O38− was 183 ± 5 Å2. This
observation suggests that the larger structural isomers of anions
for sizes m = 13−19 may have structures similar to those of
cations.
4. CONCLUSION
In this study, we have observed abundant compositions of
vanadium oxide cluster cations and anions as a result of
collision-induced dissociation products formed at the inlet of
the ion drift cell. The compositions had a dependency on the
even and odd number of vanadium atoms. The compositions
predominantly found for cations were (V2O4)(V2O5)(m−2)/2+
for even size and (VO2)(V2O5)(m−1)/2+ for odd size; similarly,
the compositions found for anions were (V2O5)m/2− and
(VO3)(V2O5)(m−1)/2−. These representative compositions have
been proposed for the first time and were found to be
applicable at least to mass number up to 2000 (approximately
m = 20).
The structures of the even and odd sized cluster ions were
also predicted by quantum chemical calculations for the
geometries based on previous studies for m = 2−12. The
right polygonal prism structures were calculated for even sized
cluster cations and anions; pyramid and bridged structures were
H DOI: 10.1021/acs.jpca.6b03403
Article
proposed for odd sized cluster ions. Experimental collision
cross sections of the vanadium oxide cluster cations and anions
have been measured using ion mobility mass spectrometry. To
assign the structures of the cluster ions of the size m = 2−12,
comparisons between experimental CCSs and theoretical CCSs
from proposed structures were made. As a result, CCSs of even
sized cluster cations (m = 6−12) were assigned to be the right
polygonal prism pattern, except that m = 12 was also
polyhedron; odd sized ones (m = 5−11) were assigned to be
bridged structures. The even sized cluster anions (m = 6−10)
were assigned to be right polygonal prism structures, and odd
sized ones (m = 5−11) were assigned to be pyramid structures.
Here, we experimentally confirmed a structural growth pattern
for the cluster ions with even number and odd number of
vanadium atoms, whether growing by increasing the size of
polygonal prism or by expanding the sizes of bridged and
pyramid structures. On the other hand, due to a structural
transition found for anions at around m = 12, which can be
clearly observed in the ATD plot and mass versus arrival time
plot, a captured typed structure was proposed and fitted to the
experimental CCS. The proposed captured typed structure
suggested the cluster anion of m = 12 has a higher density than
the cluster cation, and such a structure should be considered for
cluster anions of m ≥ 12.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpca.6b03403.
Estimation of the total internal excitation energy, arrival
time versus mass 2D plot of vanadium oxide cluster
cations and anions, and the complete author list of ref 35
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
*Tel.: +81 22 795 6577. E-mail: misaizu@m.tohoku.ac.jp.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by a Grant-in-Aid for Scientific
Research from the Japan Society for the Promotion of Science
(JSPS), the Research Seeds Quest Program (JST), and the
Murata Science Foundation. Theoretical calculations were
partly performed using the Research Center for Computational
Science, Okazaki, Japan.
■
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