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Chemical Physics Letters 608 (2014) 295302

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Chemical Physics Letters


journal homepage: www.elsevier.com/locate/cplett

The boron conundrum: Bonding in the bowl B30 and B36, fullerene B40
and triple ring B42 clusters
Hung Tan Pham a, L.V. Duong a, Nguyen Minh Tam a,b, M.P. Pham-Ho a, Minh Tho Nguyen b,
a
b

Institute for Computational Science and Technology (ICST), Quang Trung Software City, Ho Chi Minh City, Viet Nam
Department of Chemistry, University of Leuven, B-3001 Leuven, Belgium

a r t i c l e

i n f o

Article history:
Received 14 April 2014
In nal form 23 May 2014
Available online 7 June 2014

a b s t r a c t
Geometries and bonding of B30, B36, B40 and B42 clusters were studied using quantum chemical computations. The bowl B30 and B36 and planar B42 clusters exhibit disk aromaticity. Diatropic ring current is
strong in B30 and weaker in B42. A fullerene-like B40 (D2d) having two hexagons and four heptagons
was found as the lowest-lying isomer. Such a fullerene whose MOs closely mimic those of the buckyball
B80, represents novel structural feature of boron clusters. The most stable B42 (C2h) isomer is a triple ring
tube with consistent r + p diatropic magnetic responses making it a tubular aromatic species.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Boron compounds continue to provide us with full of surprise
about their structural features. Regarding boron clusters, a plethora of two-dimensional (planar, quasi-planar) and three-dimensional (tubular, cage, spherical, fullerene. . .) shapes apparently
suggests several distinct growth patterns. Extensive effort has been
devoted to the search for new forms of boron allotropes and
nanocages [1,2], and most boron clusters appear to exhibit
polymorphism and multi-center bonding [3,4]. In relation to C60,
particular attention has been paid on the boron buckyball B80 [5],
and larger fullerene derivatives such as B100 and B112 [6] have been
predicted by computations. Some smaller all-boron fullerenes have
also been identied by computations including B14 [7], B32, B38, B44,
B50 and B56 [8,9], B40, B48,. . . (B32+8k, with 0 6 k 6 7) [10]. In many
cases, the fullerene-like form reported is however not the most stable isomer of the size considered. In addition, the buckyball B80 has
so far not been detected by experiment yet [11].
Boron has been proved to be a rare element whose atomic Bn
clusters retain either planar or quasi-planar (QP) geometries even
when the cluster size n goes up beyond >20, depending on the
charge state. The cations Bn+ prefer to adopt 3D structures at smaller sizes (at n  18) [12,13], whereas the anions Bn and dianions
Bn2 species tend to have planar or QP structures with n being
up to >30. There is an effective charge effect in which addition of
extra electrons consistently favors QP boron cluster anions, and
removal of electrons leads to 3D cations [14].

Corresponding author. Fax: +32 16 32 79 92.


E-mail address: minh.nguyen@chem.kuleuven.be (M.T. Nguyen).
http://dx.doi.org/10.1016/j.cplett.2014.05.069
0009-2614/ 2014 Elsevier B.V. All rights reserved.

Let us briey summarize the main geometrical features of the


bare clusters Bn, with n being an even number, in their neutral
state: (i) most of the sizes up to B18 have planar or QP geometries
[1518], except for the surprising B14 fullerene [7]; (ii) the most
stable B20 isomer is a tubular double ring (DR) in which the two
10-membered rings are connected together in an antiprism
bonding motif [19]; (iii) Similar to B20, each of the neutrals B22,
B24, B26 and B28 also exists in a DR ground state [20,14]. These
observations resulted in a popular belief that intermediate-sized
Bn with n P 30 still prefer tubular geometries; (iv) we recently
found that B30 has a bowl structure [21] which is composed of a
pentagon base and successively built up by two strings of 10 and
15 boron atoms yielding a vefold symmetry (C5v). This
5@10@15 strings bowl turns out to be 5 kcal/mol more stable
than the tubular 310 triple ring (TR). The slightly higher thermodynamical stability of the bowl B30 has been shown to arise from
its disk aromatic character [22,23]. In spite of its non-planarity,
the 20 P-type electrons of bowl B30 are distributed in a way similar
to those of the planar disk aromatic B2
20 dianion [25,26]. Although
the bowl B30 is not established yet as the lowest-lying isomer, it
constitutes an appropriate building-block whose recombination
eventually leads to B80 and larger buckyballs [24], (v) previous
computations [19,24] also predicted that B32 has a DR shape composed of two 16-membered ring. There is no previous report on the
B34 isomers yet, but it seems that the latter seemingly has the lowest-lying DR structure, and (vi) more recently, B36 has been found
by computations to have a bowl structure which is based on a hexagonal background and successively caped on it by two strings of
12 and 16 B atoms. The 6@12@18 strings thereby lead to a sixfold
symmetry (C6v) bowl form which is calculated to be the lowestlying structure being 20 and 32 kcal/mol more stable than the

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H.T. Pham et al. / Chemical Physics Letters 608 (2014) 295302

triple ring (TR) 312 and QP (having a hexagon and a heptagon)


isomers, respectively [25]. Existence of the neutral B36 was indirectly detected from a photoelectron spectrum of B
36 anion [25].
As far as we are aware, no careful search on the neutral B38 is
reported yet. Only a B38 cage [8] and a fullerene structure [26] were
mentioned but without a clear status (whether it is a lower-lying
isomer).
In this context, a legitimate question is as to whether the bowl
B36 also has a disk aromatic character, and the bowl shape persists
as a general structural feature of B-clusters. The following bowl
candidate is an isomer of the B42 size consisting of a superposition
of the 7@14@28 strings with a heptagon base.
Although a fullerene B40 was previously reported as a member of
the B32+8k series of clusters [10] which is based on four-membered
rings, no thorough search for structures of this size has been
explored. If conrmed, the point of interest is about the stability
of such B40 fullerene. Motivated by such key issues, we set out to
perform in the present Letter an investigation on some Bn clusters
with n = 30, 36, 40 and 42 in their neutral state. Using DFT methods,
we nd a fullerene-type form as the lowest-lying isomer of B40, but
the one located in this Letter differs much from that reported in Ref.
[13]. For its part, B42 turns out to have a tubular TR form as the
ground state. A B42 isomer formed by 7@14@21 strings also exists,
but is less favored than the TR counterpart, and more importantly,
such a B42 isomer becomes a planar disk (C7v).
In the present Letter we report for the rst time some new
geometrical features of both B40 and B42 clusters, and also an analysis of chemical bonding of B30, B36, B40 and B42. We make use of
the partition of the electron densities and the magnetic ring
currents in order to probe their bonding pattern and aromatic
character.
2. Computational methods
Standard electronic structure calculations are carried out using
the GAUSSIAN 09 program [27]. Due to the relatively large cluster
sizes, only DFT methods are employed in the searches for equilibrium structures, and subsequent determination of relative energies. The searches for energy minima are conducted using two
different approaches. In the rst, we use a stochastic genetic algorithm to generate all possible structures [14,28]. The equilibrium
structures that are initially optimized using computations with
small basis sets, are reoptimized using larger basis sets. In the second approach, initial structures of a Bn cluster are manually constructed by adding necessary B-atoms at all possible positions on
surfaces of the Bn2 or smaller clusters. The use of the genetic algorithm is effective for producing non classical 3D structures
whereas the manual search is more focused. While the large number of initial structures makes the genetic search more tedious,
only a combination of different search approaches allows new
structures to be discovered and a consistent set of lower-energy
structures to be obtained.
Previous calculations demonstrated that the B3LYP functional
underestimates the energy differences between 2D and 3D boron
clusters [18,2931]. In recent studies, we found that the TPSSh
functional gives better results on relative energies of boron clusters
than other available functionals, as compared to the high accuracy
MO method (such as CCSD(T)) [13,14]. While computations on initial guess geometries are carried out using the hybrid TPSSh functional [27], in conjunction with the 3-21G and 6-31G(d) basis sets,
all selected equilibrium geometries with relative energies up to
3 eV are fully optimized using the same functional but with the
larger 6-311 + G(d) basis set [32]. In order to conrm the identity
of true local minima obtained, their harmonic vibrational frequencies are also calculated at the same level of theory. For the analysis
of chemical bonding, in particular the aromaticity, we make use of

canonical MOs, electron localization function (ELF) [33] and electron localizability indicator (ELI-D) [34] maps, as well as the magnetic ring current approach [35] along with the ipsocentric model
[36,37]. Calculations of magnetic responses and ring currents are
carried out using the Gamess-UK program [38] in conjunction with
the SYSMO package [40].
3. Results and discussion
The calculated results are mainly presented in different gures.
Figures 1 and 2 are devoted to the bowl-shaped clusters, Figures 3
5 are for B40 and Figures 68 for B42.
3.1. Disk aromaticity of the bowl B30 and B36 and disk B42 clusters
Figure 1 displays in two different views the shape of B30 30.b,
B36 36.b and B42 42.b, in which b stands for bowl. Cartesian
coordinates of their optimized structures are given in the Supplementary Information (ESI) le. The main characteristic is that the
base of the bowl is successively enlarged from 5 in 30.b to 6 in
36.b and then 7 in 42.b. In each cluster, the number of B-atoms
in the outer string is a multiple of that of the inner base. The Batoms in each string are thus increased from x to 2x and then 3x,
with x = 5 in 30.b, 6 in 36.b and 7 in 42. Both clusters 30.b and
36.b were reported to be the lower-lying isomers of B30 (C5v)
[21] and B36 (C6v) [25], respectively. Their geometries are abundantly discussed and thus do not warrant further comments. Let
us however note that incorporation of six extra boron atoms into
the bowl brings in four p electrons in such a way that 30.b, 36.b
and 42.b contain 20, 24 and 28 valence p electrons, respectively.
The B42 42.b displayed in Figure 1 is thus composed of three circles containing 7, 14 and 28 boron atoms having the same origin,
and turns out to be a planar disk (C7v). Starting from a bowl form,
geometry optimization invariably leads to a planar form (or nearly
planar depending on the basis set employed). It appears that a heptagon base becomes large enough to overcome the inherent strain
in a bowl shape, and nally makes the cluster planar. However, as
given in a following section, 42.b is not the global minimum of B42,
being 13 kcal/mol above the corresponding tubular TR (value at
TPSSh/6-311 + G(d) + ZPE).
We now analyze the aromatic character of both 36.b and 42.b
using the same approach described before for 30.b [21]. The concept of disk aromaticity, which has been described in detail in
our recent work [2123], is based on a simple model of a particle
in a circular disk, in which a free particle is moved on a planar disk
encircled by innite walls. In polar coordinates, the Schrdinger
equation for this electron is written as follows:

!
h2 @ 2 1 @
1 @2


Wu; r EWu; r
2l @r 2 r @r r2 @ u2

where r = R is the radius of the disk, the Plank constant and l the
mass of particle. Because of the circular symmetry, the Wu; r can
be written as R(r).U(u), with U(u) = exp(imu)/(2p)1/2. The cyclic
boundary condition requires the angular part to be periodic. As a
result, the cylindrical quantum number must be integer, namely
m = 0, 1, 2,. . . Substitution into the Schrdinger equation gives
us the radial part, with 2k2 = 2lE:



@ 2 Rr 1 @Rr
m2
2
Rr 0

k

@r 2
r @r
r2

This equation is well known as the Bessels differential equation, and its solutions are the integer Bessel functions Jm(kr) [39].
The potential wall at r = R requires the radial function to vanish
at the boundary of the box, Jm(kR) = 0. The radii that correspond
to the zeroes of the Bessel function are denoted as am,n, that are

H.T. Pham et al. / Chemical Physics Letters 608 (2014) 295302

B330
330..b C5vv

B366
366.b
b C6 v

297

B42
422.b
b C7vv

Figure 1. Molecular structures (TPSSh/6-311 + G(d)) of the bowl B30 30.b, bowl B36 36.b and planar B42 42.b, from two different views.

Figure 2. Calculated p MOs of the bowl-shaped B30 30.b (C5v) and B36 36.b (C6v) and planar B42 42.b (C7v) clusters, and shape of orbitals derived from the model of a particle
on a circular disk (upper panel).

dimensionless. In this case, n is a radial quantum number that


counts the zeroes. The Bessel zeroes give rise to the quantied
energies as:

h2 am;n 2
2lR2

with : n 1; 2; 3; . . .

m 0; 1; 2; 3; . . .


3

Rotational quantum numbers are usually denoted by Greek letters as m = r, p, d, /, c. . . States with non-zero values for m will be
twofold degenerate. The lowest eigenstates in ascending ordering
are 1r, 1p, 2r, 1d, etc. (cf. Figure 2). The orbital ordering depends
on the radius of the disk. A molecule containing a number of

electrons which fully occupy degenerate eigenstates of the model


is disk aromatic. These numbers are 2, 6, 10, 12, 16, 20, 24, 28. . .
A species containing a number of electrons which only singly
occupy one of two highest degenerate eigenstates will be disk
antiaromatic. The numbers are 4, 8, 14, 18. . .
Figure 2 displays a comparison of the shapes of selected p MOs
of 30.b, 36.b and planar 42.b. The 2pz atomic orbitals recombine to
give delocalized p MOs, and their shape is not susceptible to the
structural composition. The orbital plots show a strong resemblance within the sequences. 30.b contains 20 valence p-electrons
that fully occupy 10 orbitals (cf. Ref. [21]). The 24 valence
p-electrons of 36.b and 28 valence p-electrons of 42.b also fully
occupy degenerate MOs. In this case, the two additional MOs of

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H.T. Pham et al. / Chemical Physics Letters 608 (2014) 295302

b)) MOs

a) Tootall

cc) - MO
MOss

d H
d)
HO
OM
M 2
MO

e)) H
HO
OM
MO
O-1 1

(d
deggen
nerratee
)

(d
deggen
nerratte
)

Figure 3. Characteristics of the planar disk B42 42.b (C7v). Current density maps computed using HF/6-31G(d) wavefunctions: (a) total p + r, (b) p and (c) r electrons. Shape
of (d) HOMO and (e) HOMO-1.

400.11

4400.22

440..3

40.44

D2d - 1A1

Cs - 1A
A'

Cs - 1A'
A

D20dd - 1A1

00
0.0

144.33

224..6

28.99

Figure 4. Some lower-lying isomers of B40. Optimized geometries, point groups, electronic states and relative energies (in kcal/mol obtained from TPSSh/6-311 + G(d) + ZPE
computations).

36.b belong to the 1c orbitals, and those of 42.b to the 2d orbitals


of the disk model. For the sake of clarity, Figure 3 displays again the
degenerate HOMO (2d) and HOMO-1 (1c) of 42.b.
When using the classical Hckels rule, these species can be
considered as antiaromatic (4N electrons, N = 5, 6 and 7). However,
as the valence p-electrons of each disk fully occupy the corresponding lowest-lying eigenstates (Figure 2), the model of a particle in circular box confers to each isomer a disk aromatic character:
B30 30.b with n = 2, l = 1. . . (1r)2 (1p)4 (1d)4 (2r)2 (2p)4 (1/)4,
B36 36.b with n = 1, l = 4. . . (1r)2 (1p)4 (1d)4 (2r)2 (2p)4 (1/)4
(1c)4, and
B42 42.b with n = 2, l = 2. . . (1r)2 (1p)4 (1d)4 (2r)2 (2p)4 (1/)4
(1c)4 (2d)4.
In order to probe further their aromaticity, we plot the ring current maps that are the response of a molecule with respect to an
external magnetic eld. The ring current of 30.b has been discussed in our previous Letter [21]. The ring current maps of 30.b
and 36.b are presented in Figure S1 of the ESI le. Here we display
in Figure 3 only the ring current of 42.b. The ipsocentric model is

an effective model which was used to evaluate aromaticity of planar compounds [40,41]. In the framework of this model, an excitation from an occupied to an unoccupied molecular orbital can
result in a contribution to the ring current which can be either diatropic, paratropic or null. Accordingly, a diatropic current arises if
the product of symmetries of occupied and unoccupied orbitals
contains the in-plane translational symmetry. A paratropic
response to an external magnetic eld results when the product
of symmetries of occupied and unoccupied orbitals contains the
in-plane rotational symmetry. This rule is relatively straightforward for planar species.
The electron density of each species can be partitioned in terms
of r and p electrons. The main difference between the clusters considered in that 30.b has only diatropic current for all components.
36.b presents a conicting response, with a paratropic current from
p electrons but a diatropic current from r electrons. The resulting
total current shows a paratropic response along the inner 6-ring
and the outermost 18-ring, and a diatropic along the central 12-ring
(Figure S1, ESI). It is clear that more appropriate plots for visualising
the current of bowl structure [42] need to be carried out before a
clearer picture for both 30.b and 36.b can be obtained.

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H.T. Pham et al. / Chemical Physics Letters 608 (2014) 295302

nall faace
H xaagoon
Hex

Heptaagoon
nall hol
h le

aa) LUM
MO
MO

b
b) HO
H MO
MO

c) EL
LII - Dtootal

d E
d)
EL
LI - D

E
EL
LII - D

Figure 5. Characteristics of the fullerene B40 40.1 (D2d). Frontier orbitals (a) HOMO a1 and (b) LUMO b2 viewed in two different faces. Electron localizability indicator maps (c)
ELI-Dtotal, (d) ELI-Dr and (e) ELI-Dp viewed from a heptagonal face.

For its part, the planarity of 42.b provides us with clear-cut ring
current maps (Figure 3). Its 28 delocalized p electrons are effective
for the magnetic response of their density, and the total current
includes all core, p and r MOs. They induce a relatively weak contribution to the total ring current. The r electrons induce a stronger diatropic current around each boron center, and the total ring
current mainly arises from contributions of r electrons. In particular the inner 7-circle is locally characterized by a paramagnetic
current, irrespective of electron type, but with a predominant r
contribution. Such conicting ring currents are comparable to the
situation of the dianion B2
20 [23]. Analysis of the excitations
involved shows the main contributions arises from the transitions
HOMO ? LUMO + 1 and HOMO-1 ? LUMO (the virtual 2c/3d
pairs). It can thus be concluded that B42 42.b has a weaker disk aromatic character than B30, and that is presumably a reason for its
lower thermodynamic stability.
3.2. A fullerene-like B40: a thermodynamically stable isomer
As stated above, although the isomers of B40 size have not thoroughly been searched, a fullerene B40 form has been identied
using a leapfrog transformation [10]. A relationship between carbon and boron fullerenes can be established in that a three-connected carbon in C-fullerene can be transformed into a hexagonal
in B-fullerene. The C24+6k fullerenes can thus be transformed into
the B32+8k ones. Starting from a C10, these authors obtained by

capping a C30 which can further be modied using leapfrog giving


B40 [10]. Nevertheless, the identity of such B-fullerenes (global or
local minimum) could not be determined. For example, a B32 (Oh)
fullerene was found, but for this size a DR 216 isomer was found
to be by far the lowest-lying isomer [24].
We carry out a search for B40 structures and the geometries of
some lowest-lying isomers of this size are displayed in Figure 4
(their optimized coordinates are given in the ESI le). It turns out
that the fullerene 40.1 is calculated to be the lowest-lying isomer
(of the structures located so far), being 14 and 25 kcal/mol below
both planar isomers 40.2 (Cs) and 40.3 (Cs), respectively. The DR
40.4 (D20d) is about 29 kcal/mol higher in energy than 40.1. In spite
of intensive search, we could not relocate the fullerene reported in
Ref. [10] within a relative energy of <3 eV. Accordingly, after the
fullerene-type B14 [7], the B40 40.1 represents the second boron fullerene which is the thermodynamically most stable isomer of the
corresponding size. 40.1 is mainly characterized by a high point
group symmetry (D2d, 1A1) and contains two staggered hexagonal
faces and four heptagonal faces forming a kind of distorted cylinder
connecting the two hexagons. The C2 axis is going through the two
hexagons. As in B80, each boron is a multi-coordinated centre, thus
creating about 48 triangles fullling the cylinder surface.
Figure 5 displays the frontier orbitals and ELI-D maps of 40.1. To
facilitate the comprehension, the orbitals are present in two different views through a hexagonal and a heptagonal face. The densities
of states of 40.1 that consist of the atomic contributions to the MOs

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H.T. Pham et al. / Chemical Physics Letters 608 (2014) 295302

a)) 4
42..t (C
C2hh)
siidee vview
w

ELI Dtotal
c)) E

2.tt ((C
C2h)
b
b) 42
toop vieew
w

d) ELII D

ee) EL
L I D

Figure 6. Optimized geometry (TPSSh/6-311 + G(d)) of the B42 triple ring (TR) in two different views: (a) side view, and (b) top view, and its ELI-D isosurfaces: (c) total p + r
electrons, (d) p electrons, and (e) r electrons.

c)) tottall +

b) ellecctrron
ns

a)) eleecttroons

Figure 7. Maps of magnetic responses of the triple ring B42 42.t (C2h). Contributions are from (a) r electrons, (b) p electrons, and c) total r + p electrons (HF/6-31G(d)).

=5

=3

LUMO

LUMO + 1

=4
=2
HOMO 1

HOMO

Figure 8. Main excitations responsible for the magnetic responses of the triple ring B42 42.t (C2h).

H.T. Pham et al. / Chemical Physics Letters 608 (2014) 295302

(given in Figure S2 of the ESI le) clearly point out that several
HOMOs are built up mainly from px/py and in part from pz atomic
orbitals. The contributions of s atomic orbitals appear to be negligible in the ten highest energy MOs. Although the cage is not having an icosahedral form, both degenerate HOMO (a1) and LUMO
(b2) shown in Figure 5 contain some features closely mimicking
those of the boron buckyball B80 or even those of C60 [43]. The
orbital lobes are mainly distributed over the triagonal faces
without components around the 6- and 7-faces, and located outside the cage surface. The energy gap between the HOMO and
LUMO of 40.1 amounts to 3 eV (Figure S2 of ESI), which is much
larger than that of 2 eV in the boron buckyball B80 [43,44], thus
making the species kinetically stable or the excitation is expected
to lie in high energy spectrum.
The electron localizability indicator (ELI-D, Figure 5ce) is a
simple measure of the electron localization in a molecular system
and thus gives information about the molecular spaces, called
basins, where electrons are likely to occupy. It is useful to address
localization domains which correspond to cores, bonds or lone
pairs. The ELI-D description can also be partitioned into different
r and p components, and this bonding description is comparable
to the picture given by the electron localization function (ELF)
approach. It can be seen that both type of electrons, either p or
r, equally contribute to the bond formation around the faces of
the fullerene. Although integration of electron densities over the
basins leads to the corresponding populations, we are not able in
this case to assign the electron numbers to the basins, due to the
complex and ambiguous electron distribution. Note that from the
ELI-D(total) map, there is in 40.1 a bond between two adjacent
boron atoms.
In summary, the existence of both hexagonal and heptagonal
faces in 40.1 represents a novel geometrical feature of boron fullerene, and this aspect deserves more detailed examination in subsequent studies.
3.3. B42 triple ring: a tubular aromaticity
Let now examine the B42 cluster. As stated in Section 3.1, the
planar disk 42.b is calculated to be less stable than the triple ring
(TR) 42.t whose optimized geometry is presented in Figure 6, again
in two different side and top views. 42.t is composed of three
strings of 14 boron atoms connected each other in an antiprism
motif (C2h). Such an arrangement creates several triangular, rhombic and hexagonal faces. Each hexagon is apparently doped at the
center by an atom giving rise to a block of B7. The distance between
two strings amounts to 1.50 , which is slightly larger than the
distance of 1.35 between the two strings of the corresponding
DR 42.d formed by two strings of 21 (221) B-atoms. The TR 42.t is
calculated at 13 kcal/mol more stable than the disk 42.b and
53 kcal/mol more stable than the DR 42.d (values at TPSSh/6311 + G(d) + ZPE).
Figure 6 also displays the ELI-D maps of 42.t. The map of densities of states are given in Figure S4 of the ESI le. The r electrons
are mainly located in tangential orbitals, connecting the B-atom of
each string (Figure 6c). The p MOs, arising from radial atomic orbitals, are mostly delocalized also along each atom string but pointing toward outside the tubular surface (Figure 6d). The sum of
contributions of both types of electrons, as seen in Figure 6e,
clearly result in the basins located between each boron-boron
bond within either each string or between two strings. The energy
gap between both frontier orbitals of the TR 42.t amounts to
1.6 eV, which is close to that of 1.4 eV of the planar 42.b.
Figure 7 displays the maps of the magnetic ring currents of 42.t
due to the contributions of r electrons (Figure 7a) and p electrons
(Figure 7b) and of the total density (Figure 7c). It is obvious that
consistent and unambiguous responses occur inducing strong

301

diatropic current, irrespective of the electron type. Excitations


within the frontier orbitals, as shown in Figure 8, namely
HOMO ? LUMO + 1 and HOMO-1 ? LUMO, bring in essential contributions to magnetic responses. The change of the K number
accompanying these electronic transitions obeys the selection rule,
DK = 1, thus making the TR tube aromatic. A similar situation was
previously observed in the boron toroids, that are in fact the double
ring structures of B20, B24, B28 characterized by a double aromaticity [19,29,45]. We would conclude that the B42 TR exhibits a tubular aromaticity, which is seemingly a general feature of boron
hollow cylinders. Such a tubular aromatic character tends to stabilize thermodynamically the boron tubes and thereby makes them
lower-lying isomers.
4. Concluding remarks
In the present theoretical study, we determined the geometries
and chemical bonding phenomena of some boron clusters Bn with
n = 30, 36, 40 and 42 in their neutral state using density functional
theory and molecular orbital computations. The most important
results emerge as follows:
(i) The bowl-shaped clusters B30, B36 and the planar disk B42
were conrmed to have a disk aromatic character. This is
strong in bowl B30 with consistent diatropic ring current.
The weaker disk aromaticity in planar B42 makes it thermodynamically less stable,
(ii) A fullerene type having two hexagons and four heptagons
was identied as the lowest-lying isomer of B40. The MOs
of this B40 fullerene closely mimic those of the buckyball
B80. The presence of both hexagonal and heptagonal faces
in a boron fullerene represents a novel structural aspect
which deserves to be investigated further, and
(iii) The B42 cluster exhibits a triple ring as its lowest-lying isomer, which is slightly energetically more stable than the planar disk. The triple ring B42 is characterized by a consistent
diatropic response to external magnetic eld. Such a characteristic tubular aromaticity contributes to its high thermodynamic stability.
Overall, it appears that stabilized fullerene-type and tubular
cylinder are frequently occurred in boron clusters Bn in the size
range of n P 40, and their typical formation and specic bonding
foreshadow different growth paths leading to larger cages, fullerenes and tubes. Further investigations on larger boron clusters
could allow these patterns to be established.
Acknowledgments
We are grateful to the Department of Science and Technology of
Ho Chi Minh City, Vietnam, for granting major research projects at
ICST. MTN is indebted to KU Leuven Research Council (GOA and
IDO programs) for continuing support. We appreciate the help of
Remco Havenith in plotting the ring current maps, and the valuable discussion with Arnout Ceulemans on the boron conundrum.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.cplett.2014.
05.069.
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