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Prediction and characterization of a new kind of alkali–superhalogen

species with considerable stability: MBeX3 (M = Li, Na; X = F, Cl,
Br)w
Song-Hua Cui, Ying Li, Fang-Fang Wang, Di Wu* and Zhi-Ru Li
Received 10th July 2007, Accepted 30th August 2007
First published as an Advance Article on the web 13th September 2007
Published on 13 September 2007. Downloaded by Temple University on 27/10/2014 13:49:16.

DOI: 10.1039/b710536c

The geometries of the MBeX3 (M = Li, Na; X = F, Cl, Br) series with all real frequencies are
reported using the B3LYP and MP2 methods with the 6-311+G(d) basis set. The natural bond
orbital (NBO) and atom in molecule (AIM) analyses indicate the ionic character of the M–X
bonds connecting the alkali atom M and the superhalogen BeX3. The introduction of a
counterion M+ only slightly affects the geometry of BeX3
, but produces a more stable species.
The bond energies (Eb) and vertical ionization potentials (VIP) of the MBeX3 species are obtained
at the CCSD(T)/6-311+G(3df) level. These alkali–superhalogen species exhibit large Eb
(130.4–222.3 kcal mol
1) and VIP values (9.46–14.05 eV) to show considerable stabilities. In
addition, both Ebs and VIPs of MBeX3 are found to be closely related to the electronegativity of
the X ligands and partial atomic charges.

1. Introduction when a simple formula for a class of high EA species MXk+1

In the last decades, enormous progress has been made in the
synthesis, characterization, and fundamental understanding of
materials using atoms as building blocks of matter. Never-
theless, in a precursory theoretical work, Khanna and Jena1
proposed that clusters with simultaneously closed atomic and
electronic structures can be considered as superatoms and
serve as building blocks for cluster-assembled solids. Ever
since Al13K was predicted to form an ionically bound supera-
tom complex that would resemble a familiar halogen salt,2
superatoms have become basic units in chemistry and at-
tracted more and more attention. Most recently, the Castle-
man group demonstrated the superatom characteristics of Al13
and Al14 clusters in two classes of gas-phase aluminum–iodine
clusters, and indicated that superatoms indeed had synthetic
utility and would represent potential building blocks for the
assembly of novel nanostructured materials.3,4 Therefore, the
research on superatoms will provide compounds with novel
structures, special bonding natures and properties, and thus
promote the development of chemistry (including nanometer
chemistry and supramolecular chemistry) and materials science.
A well-known subset of superatoms is superhalogen5–12 that
is capable of exceeding the 3.617 eV (Cl)13 atomic electron
affinity (EA) limit due to collective effects. Although super-
halogens have been known and have been of interest since the
early 1960s, they were first named ‘‘superhalogens’’ in 1981,
State Key Laboratory of Theoretical and Computational Chemistry,
Institute of Theoretical Chemistry, Jilin University, Changchun,
130023, China. E-mail: wud@mail.jlu.edu.cn; Fax: (+86) 431-
88498026
w Electronic supplementary information (ESI) available: Optimized
geometries, the Laplacian of the electron density at a bond critical
point of the NaBeX3 (X= F, Cl, Br) species. See DOI: 10.1039/
b710536c
(M is a main group or a transition metal atom, X is a halogen
atom or a monovalent group with high EA such as CN, and k
is the maximum formal valence of M) was proposed.6 Super-
halogen anions such as BF4
, AlCl4
and AsF6
are com-
monly found as fragments in gas-phase molecules and in
crystalline solids. Besides, superhalogens involving alkaline
earth atoms have been studied by several groups.12,14–17
Recently, Skurski and co-workers performed extensive studies
on several alkali earth halide superhalogen species,14,17 MX3

(M = Be, Mg, Ca; X = F, Cl, Br), as well as species with mixed
halide ligands. All MX3
species exhibit large electron binding
energies that significantly exceed the EA of chlorine. Most
recently, Wang et al. reported a joint experimental and theore-
tical investigation on four alkali earth halide superhalogens
MX3
(M = Mg, Ca; X = Cl, Br), using photoelectron
spectroscopy (PES) and ab initio calculations.12 Good agreement
was obtained between the experimental and theoretical data.
Superhalogens are of great importance in chemistry, since
they can be used for the oxidation of counterpart systems with
relatively high ionization potentials (IP) (such as O2, Xe) and
allow the synthesis of unusual chemical compounds. In addi-
tion, superhalogens have been widely used in the production of
organic superconductors.5,10 Considering the high EA of
superhalogens, it is reasonable to expect that they serve as
components of novel nontraditional alkali–superhalogen solid
salts to mimic the well-known alkali–halogen salts. Thus, the
characterization of the interaction between an alkali atom and
a superhalogen and the prediction of the properties of such
species should be a meaningful project. However, as far as we
know, except the Al13X (X = alkali atom) species, the study of
other alkali–superhalogen species has not yet been reported.
In the present work, we chose superhalogen BeX3 to interact
with alkali atoms and theoretically predicted a novel series of
alkali–superhalogen species MBeX3 (M = Li, Na; X = F, Cl,

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Br). The main objective of this paper is to (1) explore the
preferred orientations between the alkali atom and the planar
superhalogen BeX3, (2) reveal the bonding nature between M
and BeX3, (3) analyze the relationship between bond energies
of the MBeX3 and alkali atomic size, electronegativity of the X
ligands and the partial atomic charge, and observe which of
the IP and atomic size of the alkali atoms plays a dominant
role in the bond strength to superhalogen BeX3, and (4)
exhibit the considerable stabilities with large vertical ioniza-
tion potentials (VIP) of the MBeX3 species and show the
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correlation between VIPs and electronegativity of X ligands
and the partial atomic charge on the Be atom. This work
should be interesting for future theoretical investigations and
experimental work.
2. Computational methods
The geometries of a series of MBeX3 (where M = Li, Na; X =
F, Cl, Br) species with all real frequencies were optimized by
the B3LYP and MP2 methods,18–21 with the same basis set
6-311+G(d).
Natural bond orbital (NBO)22,23 and atoms in molecules
(AIM)24 analyses at the MP2 computational level were per-
formed to provide an insight into the bonding nature of these
MBeX3 species.
The vertical ionization potential (VIP) and intramolecular
interaction energies (Eint) between M and BeX3 subunits for
these MBeX3 species were calculated at the CCSD(T)/6-
311+G(3df) computational level. We used the counterpoise
(CP) procedure25,26 to eliminate the basis set superposition
error (BSSE) effect given by eqn (1):27
Eint ¼ EAB ðXAB Þ
EA ðXAB Þ
EB ðXAB Þ ð1Þ
where the same basis set, XAB, was used for the subunit
energies (EA and EB) calculation as for the complex energy
(EAB) calculation. However, there is an additional contribu-
tion appearing in the interaction energy that has a more
crucial impact, namely, the deformation energy contribution
due to the structural deformation of the complex subunits
upon complexation. To estimate the extent of the contribution
of the deformation on the computed interaction energies, we
use the approach suggested by Duijneveldt and coworkers28
def
Eint ¼ EMBeX3
½EM þ ðEBeX3 þ EBeX 3
Þ ð2Þ
def
where EBeX describes the energy associated with the structural
3 the MP2/6-311+G(d) level. In our work, the Be–Fb bond
change of the superhalogen BeX3 upon complexation.
All calculations were performed using the GAUSSIAN 03
program package.29
3. Results and discussions
3.1 Structural characteristics of the MBeX3 species
The optimized geometrical structures of the LiBeX3 (X = F,
Cl, Br) species at two levels, B3LYP/6-311+G(d) and MP2/6-
311+G(d), are displayed in Fig. 1, and those of the NaBeX3
species are shown in Fig. S1 of the ESI.w The symmetries and
lowest frequencies of these species are shown in Table 1. It can
easily be seen from Table 1 that the MBeX3 species show large
5722 | Phys. Chem. Chem. Phys., 2007, 9, 5721–5726
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HOMO–LUMO gaps ranging from 8.99 to 14.98 eV, suggest-
ing that they all may be thermodynamically stable. From
Fig. 1 and Fig. S1,w the geometrical parameters of the MBeX3
species at the B3LYP level agree very well with those at the
MP2 level, so the MP2 structures were used for further
calculations and discussions.
We know LiF and NaF are simple linear molecules with
CNv symmetry, while the situation becomes a bit complex
when an alkali atom interacts with the planar superhalogens
BeX3 (X = F, Cl, Br) because the reactive site of the latter
could be apex, side or face. In our calculations, all possible
orientations between M and BeX3 have been considered.
Interestingly, the alkali atom is always found to occupy the
side site of BeX3 even though the starting geometries included
the alkali atom occupying the apex or face sites. Consequently,
all the MBeX3 species exhibit planar structures with two M–X
bonds connecting the alkali atom with BeX3.
From Fig. 1, 18 structures of the LiBeX3 (X = F, Cl, Br)
species were obtained at the MP2/6-311+G(d) level. Herein,
LiBeF3, LiBeCl3 and LiBeBr3 possess C2v symmetries (a–c).
Each of the LiBeX2X 0 (X a X 0 ) species (d–o) has two isomers
with C2v and Cs symmetry, respectively, along with different
Li–X bonds formation. For example, there are two isomers for
LiBeF2Cl, that is, the Li atom connects to BeF2Cl by two Li–F
bonds (d, C2v) or by a Li–F bond and a Li–Cl bond (e, Cs). For
LiBeFClBr, three isomers (p–r) with Cs symmety were ob-
tained. From Fig. S1,w the NaBeX3 (X = F, Cl, Br) species
also have 18 structures, which are very similar to those of
LiBeX3. In each MBeX3 species, there are two X ligands
bonding to the M atom and a free one. For convenience, we
name the former Xa and the latter Xb.
Because of the ionic bond character between M and BeX3
(see next section), the MBeX3 species can be seen as a super-
halogen anion BeX3
in combination with a counterion M+.
On the whole, the structural integrity of BeX3
is maintained in
the MBeX3 systems. Compared with the geometries of BeX3

previously reported by Anusiewicz and Skurski,17 only a slight
influence from the counterion M+ on the BeX3
subunit is
discerned. On the one hand, upon direct interaction with M+,
the Be–Xa bonds are found to lengthen and +XaBeXa becomes
smaller. On the other hand, the counterion indirectly influences
the Be–Xb bond and leads to a shorter Be–Xb bond as com-
pared to those in an isolated BeX3
anion. Take Be–F bond for
example, Anusiewicz and Skurski had reported the Be–F dis-
tance within the 1.451–1.492 Å range for the BeX3
anions at
length of the MBeX3 species varies from 1.412 to 1.431 Å,
while the Be–Fa bonds are in the range of 1.512–1.541 Å with
the same method. In addition, the elongation of the Be–Xa bond
is more in LiBeX3 than in NaBeX3, suggesting that the influence
of Li+ on the BeX3
subunit is stronger than that of Na+.
The nature of Xb atom also slightly influences the structure
of MBeX3. The geometrical parameters shown in Fig. 1 and
Fig. S1w demonstrate that the Be–Xa distance gradually
decreases when the Xb atom is subsequently substituted with
a less electronegative halogen atom, whereas the reverse is
observed for the M–Xa bond. For example, when the Xb atom
in LiBeF3 varies in the order F - Cl - Br, the Be–Fa bond
length decreases in the order a (1.541 Å) 4 d (1.534 Å) 4 f
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Fig. 1 The optimized geometries (bond lengths in Å, bond angles in 1), the Laplacian of the electron density at a bond critical point r2r(r) (au) of
the LiBeX3 (X = F, Cl, Br) species.

(1.530 Å) and the Li–Fa distance shows an increasing sequence From Fig. 1 and Fig. S1,w +ClaBeCla is 109.41 and 112.61 for
of a (1.790 Å) o d (1.796 Å) o f (1.801 Å). LiBeCl3 and NaBeCl3, respectively, and +BraBeBra is 111.41
The structures of the BeX3 (X = Cl, Br) subunits in MBeX3 and 114.41 for LiBeBr3 and NaBeBr3, respectively, while at the
are also compared to the neutral BeCl3 and BeBr3 species. same MP2/6-311+G(d) level, +XaBeXa in neutral BeCl3 and

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Table 1 The lowest vibrational frequencies n1 (cm
1); NBO charges on M (Li, Na) and Be atoms; HOMO–LUMO gap (eV), bond energies Eb
(kcal mol
1), vertical ionization potential (VIP) (eV) of the MBeX3 (M = Li, Na; X = F, Cl, Br) species

Species Isomer Symmetries n1/cm
1 qBe qM HOMO–LUMO gap Eb/kcal mol
1 VIP/eV
LiBeF3 a C2v 151 1.749 0.978 14.98 205.0 13.45
LiBeCl3 b C2v 92 1.440 0.913 11.11 153.1 10.68
LiBeBr3 c C2v 71 1.348 0.897 10.10 139.4 9.84
LiBeF2Cl d C2v 140 1.632 0.979 11.04 222.3 10.80
e Cs 127 1.678 0.950 12.27 166.1 11.92
LiBeF2Br f C2v 129 1.606 0.979 9.95 205.3 9.97
g Cs 122 1.670 0.942 11.12 151.4 10.99
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LiBeCl2F h C2v 96 1.588 0.912 12.27 154.6 11.85

i Cs 119 1.547 0.950 11.09 172.2 10.76
LiBeCl2Br j C2v 86 1.401 0.914 10.07 161.8 9.90
k Cs 84 1.418 0.903 11.05 143.3 10.96
LiBeBr2F l C2v 79 1.547 0.892 11.21 141.4 10.96
m Cs 106 1.492 0.944 10.06 157.6 9.94
LiBeBr2Cl n C2v 75 1.392 0.893 11.03 140.3 10.95
o Cs 79 1.376 0.906 10.09 148.4 9.87
LiBeFClBr p Cs 111 1.510 0.951 10.03 179.5 9.95
q Cs 114 1.530 0.943 10.99 152.4 10.89
r Cs 88 1.569 0.902 11.33 144.5 11.10
NaBeF3 a C2v 71 1.749 0.991 13.83 192.4 14.05
NaBeCl3 b C2v 41 1.448 0.953 10.36 143.5 10.22
NaBeBr3 c C2v 29 1.355 0.940 9.42 130.4 9.46
NaBeF2Cl d C2v 60 1.643 0.992 10.04 188.8 11.23
e Cs 61 1.680 0.975 11.36 153.0 11.31
NaBeF2Br f C2v 53 1.621 0.992 8.99 171.3 10.30
g Cs 59 1.672 0.970 10.28 138.0 10.45
NaBeCl2F h C2v 48 1.590 0.953 11.33 145.6 11.30
i Cs 53 1.556 0.975 10.21 158.2 11.01
NaBeCl2Br j C2v 38 1.410 0.953 9.35 147.6 9.48
k Cs 37 1.425 0.946 10.42 133.2 10.50
NaBeBr2F l C2v 38 1.550 0.940 10.42 132.9 10.50
m Cs 45 1.504 0.971 9.22 143.1 10.21
NaBeBr2Cl n C2v 31 1.398 0.940 10.27 131.7 10.50
o Cs 34 1.384 0.947 9.39 137.6 9.47
NaBeFClBr p Cs 47 1.523 0.976 9.17 158.8 10.14
q Cs 49 1.539 0.970 10.11 138.7 10.37
r Cs 44 1.572 0.946 10.55 134.7 10.59

BeBr3 is calculated to be 86.41.12 Obviously, after BeX3 (X =
Cl, Br) are alkalized, +XaBeXa becomes much larger and the
BeX3 subunit shows a tendency from C2v to D3h geometry.
This also suggests the ionic character of the bonds between the
alkali atoms M and the superhalogen BeX3. However, due to
the Coulomb attraction between the negatively charged Xa
ligands and the positively charged M+, +XaBeXa could not
reach the ideal 1201 as in isolated BeCl3
and BeBr3
anions.
It is noted that the MBeX3 species has an electron-deficient
beryllium atom, which can accept pairs of electrons to com-
plete an octet if suitable coordinate covalent bond donors are
available. Therefore, during the process of experimental synth-
esis of MBeX3, the MBeX4
species have the possibility to
appear, their relative amounts depend, among other things, on
the ratio of the halogen atoms to Be.
3.2 Bonding properties of the MBeX3 species
To explore the bonding nature between the alkali atoms and
the superhalogen BeX3, NBO charge analyses were performed.
As given in Table 1, the NBO charge (0.892–0.992) on the M
(M = Li, Na) atom in each MBeX3 system is close to +1.
Thus for these MBeX3 species, the superhalogen valences are

1 for BeX3. It means that the alkali atom loses an electron to
become M+, and the superhalogen BeX3 gets the electron to
become BeX3
. Hence, the superhalogen BeX3 species behaves
like a single halogen atom when it interacts with an alkali
atom. The completely charge-separated state of these MBeX3
species implies that the bonds between M and superhalogen
BeX3 are typical ionic.
The chemical bonding of these MBeX3 species can be
further studied by atom in molecule (AIM)30 analysis. Accord-
ing to AIM theory, the Laplacian of the electron density at a
bond critical point (BCP), r2r(r) can be used to describe the
chemical bonding nature of covalent, ionic and hydrogen
bonds, and Van der Waals interactions. Kock and Popelier30,31
proposed that, for covalent bonds, the value of r2r(r) is
negative. For ionic bonds, hydrogen bonds and Van der Waals
interactions, the values of r2r(r) are positive. So we calculated
the r2r(r) values for all the M–X bonds that connect M and
BeX3 at the MP2/6-311+G(d) level. From Fig. 1 and Fig. S1,w
the results range from 0.086 to 0.341 au, also suggesting ionic
bonds between M (Li, Na) and BeX3, which agrees with the
NBO analyses mentioned above. So the NaCl-like compound
forms between the alkali atom and superhalogens BeX3 and
the MBeX3 species can be written as M+(BeX3)
.
3.3 Bond energy analyses
In this study, the bond energy (Eb) of MBeX3 is defined as the
minus value of Eint between the alkali metal M (Li, Na) and
superhalogens BeX3 subunit. Eint can be calculated by eqn (2)

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with CP correction and the deformation energies contribution.
As shown in Table 1, the Eb values of MBeX3 range from
130.4 to 222.3 kcal mol
1 at the CCSD(T)/6-311+G(3df) level
of theory. Using the same method, the bond energies for the
LiF, LiCl, LiBr, NaF, NaCl and NaBr molecules were calcu-
lated to be 133.53, 107.97, 98.00, 111.16, 94.45 and 86.36 kcal
mol
1, respectively. Clearly, the bond energies of MBeX3 are
comparable to or even larger than those of traditional ionic
bond energies, showing a strong interaction between M and
the superhalogen BeX3, and also showing the stability of these
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MBeX3 species.
Because the bonding between the superhalogen and the
alkali atom is of ionic character, where the outermost s
electron of the alkali atom is transferred to the superhalogen,
both the size of the alkali atom and its IP should play a role
in the strength of the bonding. On the one hand, the lower
the IP of the alkali atom, the stronger the binding should be
as it is less costly to transfer an electron from the alkali
atom to the superhalogen. On the other hand, since ionic
bonding would be inversely proportional to the distance
separating the alkali atom from the superhalogen, the alkali
atom with the smaller size should be stronger bound to the
superhalogen because it would come closer to the superhalo-
gen. Thus, the IP and atomic size of the alkali atoms compete
with each other as far as their bond strength to superhalogen
is concerned.
The correlation between the Ebs (see Table 1) and the
electronegativity of X ligands, partial atomic charges, or
atomic size of the M atom is analyzed in detail, and a few
tendencies could be discerned:
(i) In the MBeF3–MBeCl3–MBeBr3 (M = Li, Na) series, the
Eb value decreases in the order MBeF3 4 MBeCl3 4 MBeBr3.
This is consistent with the partial atomic charge on M (qM)
becoming less positive.
(ii) For MBeF2Cl, MBeF2Br and MBeCl2Br, the isomer
with C2v symmetry exhibits the larger Eb value than that with
Cs symmetry. This is reflected by the larger qM of the former
than that of the latter. However, the opposite is true for the
MBeCl2F, MBeBr2F and MBeBr2Cl species.
(iii) For MBeFClBr, the Eb value decreases in the order:
isomer p 4 isomer q 4 isomer r, which is accompanied again
by the decrease of the qM. Take LiBeFClBr for example,
the Eb values of isomer p, q, r are 179.5, 152.4 and 144.5
kcal mol
1, respectively, while qLi = 0.951, 0.943, 0.902 au for
p, q, r, respectively.
(iv) For LiBeX3 and NaBeX3 with the same BeX3 subunit,
the Eb order is LiBeX3 4 NaBeX3.
Summarizing the above results, we can conclude that (1) the
electronegativity of the Xa ligand plays an important role in
the strength of the bonding between the alkali atom and the
superhalogen BeX3. From the former three tendencies, the
more electronegative Xa ligands, the larger Eb value, and
consequently the stronger bonds between M and BeX3. (2) It
seems clear that the partial atomic positive charge localized on
the M atom (qM) is strongly related to the bond energies of
these MBeX3 species because of the ionic bond character
between M and BeX3. (3) The atomic size but not the IP of
the alkali atom is more dominant in the bonding between M
and BeX3. It is noted that the Li atom with the smaller size
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bonds to the superhalogen BeX3 more tightly than the Na
atom does.
3.4 Vertical ionization potentials (VIP) and counterion effect
We have calculated the vertical ionization potentials (VIP),
i.e., the energy needed to ionize an electron from the neutral
cluster without changing its geometry, of the MBeX3 species.
The results obtained at the CCSD(T)/6-311+G(3df) level of
theory are presented in Table 1.
In order to determine the usefulness and accuracy of our
theoretical treatment for calculating the VIP of these alka-
li–superhalogen species, we performed test calculations of the
VIPs of some traditional alkali–halogen molecules, whose
experimentally measured VIPs are easily obtained for compar-
isons. For example, the VIP values of the LiCl and NaCl
molecules were calculated to be 9.86 and 9.06 eV, respectively,
at the CCSD(T)/6-311+G(3df) level, which agree very well
with the experimental VIP values of 9.80 and 9.0 eV, respec-
tively.32,33 Thus we are certain of the reliability of the calcu-
lated VIPs of the MBeX3 species.
From Table 1, the VIPs of the MBeX3 species range from
9.46 to 14.05 eV, which are much larger than the earlier
reported VDEs of 5.486–7.630 eV of the BeX3
anions at
the same CCSD(T)/6-311+G(3df) level.17 This indicates that
the introduction of a counterion to the superhalogen anions
BeX3
can produce more stable species. So consideration of
the charge-compensated alkali–superhalogen species is impor-
tant for the experimentalists.
The correlation between the VIPs and the M atomic size is
not straightforward, however, the electronegativity of the X
ligands and the partial atomic charge on the Be atom (qBe) is
closely related to the VIPs of the MBeX3 species. Four
tendencies could be noticed as follows:
(i) In the MBeF3–MBeCl3–MBeBr3 (M = Li, Na) series, the
VIP value decreases in the order MBeF3 4 MBeCl3 4
MBeBr3. This is consistent with the qBe becoming less positive.
(ii) For MBeF2Cl, MBeF2Br and MBeCl2Br, the isomer
with Cs symmetry exhibits a larger VIP value than that with
C2v symmetry. This is reflected by the larger qBe of the former
than that of the latter. However, the opposite is true for the
MBeCl2F, MBeBr2F and MBeBr2Cl species.
(iii) For MBeFClBr, the VIP value increases in the order:
isomer p o isomer q o isomer r, which is accompanied again
by an increase of the qBe. Take LiBeFClBr for example, the
VIP values of isomer p, q, r are 9.95, 10.89 and 11.10 eV,
respectively, while qBe = 1.510, 1.530, 1.569 au for p, q, r,
respectively.
(iv) For a certain MBeX3 species, with the Xb atom varying
in the sequence F - Cl - Br, the VIP value gradually
decreases and qBe behaves likewise.
These tendencies show a strong dependence of the VIPs on the
partial atomic positive charge localized on the Be atom (qBe).
The larger qBe, the larger VIP values. Moreover, the electro-
negativity of the Xb ligand also plays a very important role in the
VIP values. The more electronegative the Xb ligand is, the larger
the VIP value is. That the MBeX3 species may be considered as
the MBeX2+ cation with the Xb
anion attached seems to be the
most reasonable explanation for the above conclusions.
Phys. Chem. Chem. Phys., 2007, 9, 5721–5726 | 5725

4. Conclusions
Our systematic calculations on MBeX3 (M = Li, Na; X = F,
Cl, Br) have theoretically predicted a new type of alkali–
superhalogen species. All MBeX3 species present planar struc-
tures with the alkali atom occupying the side site of BeX3. The
ionic bonds between M and superhalogen BeX3 are strong and
the MBeX3 species show large bond energies (Eb) of
130.4–122.3 kcal mol
1, which are comparable to or even
larger than those of traditional ionic bond energies. The Eb
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values of these MBeX3 species are strongly related to the
partial atomic positive charge localized on the M atom (qM).
For each MBeX3 species, the isomer corresponding to the
larger qM simultaneously exhibits a larger Eb value. In addi-
tion, it is found that the Li atom with a smaller size binds to
the superhalogen BeX3 more tightly than the Na atom does.
The introduction of a counterion M+ to the superhalogen
anions BeX3
produces more stable MBeX3 species with very
large VIP values of 9.46–14.05 eV at the CCSD(T)/6-
311+G(3df) level. The close relationship between the VIPs
and the partial atomic positive charge localized on the Be atom
(qBe) is discerned, that is, the larger qBe, the larger VIP values.
This suggests that the MBeX3 species may be considered as an
MBeX2+ cation with an Xb
anion attached. Note that such
alkali–superhalogen species have not been reported so far,
thus our work will give meaningful hints to future theoretical
investigation and experimental research, which would open a
new branch of supramolecular chemistry.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (No. 20503010, 20573043).
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