Boron Nanostructures: Boron Nitride Nanostructures
derivatives with substitution by boron and nitrogen atoms
(BN)xCn−2x (n − 2x ≥ 0), which do not depend on a used theo-
retical method of analysis and on this reason are suitable in
ab initio calculations as well as for semiempirical estimations
[238]: the difference between these energies is expressed by
the simple sign-variable sum over substituted sites.
Vibration Frequencies
According to the semiempirical MO calculations [226], the
lowest vibration frequency for (BN)12 fullerene spheroids is
estimated as 340.3 cm−1.
By another semiempirical method, MNDO, frequencies of
the vibration modes dominant over the BN fullerenes IR spec-
tra were found [27] as follows: B12N12 294 and 825 and B24N24
1356, 1336, and 772 cm−1.
Multishelled Fullerenes
In Ref. [27], it was noted that the difference between the
effective radii of the spheroidal molecules B12N12 and B60N60,
which is equal to 3.36 Å, is close to the interlayer distance
of 3.33 Å in h-BN. This analogy can be extended to bonds
at fullerene surfaces: calculating the fullerene molecules
B12N12, B24N24, and B60N60, the same authors have success-
fully used the interatomic potential of B–N interaction with
the equilibrium distance of 1.4457 Å, which corresponds to
the length of the bonds within the layers of an h-BN crystal.
By the carbothermal synthesis, multishelled fullerenes—BN
“onions”—were obtained.
Extrapolating the simplified formula of radius over all reg-
ular BN fullerenes and assuming d(n) as the intralayer bond
length in BN 3D layered crystals (1.4457 Å), their radii were
calculated. Then, assuming interwall distances as interlayer
bond length in BN 3D layered crystals (3.3306 Å), their most
stable aggregates in the form of double-shelled fullerenes
were predicted [90–94]. From the obtained values, one can
find that for regular fullerenes with indices of n + 3 and n,
deviations of the difference between radii from the expected
intershell distance value are almost zero. This result does not
seem accidental. Maybe, the formula obtained for fullerene
radius reveals general relation between intralayer and inter-
layer structural parameters a and c in all the layered boron
nitride structures, such as layered crystals, multiwalled
nanotubes, and multishelled fullerenes, c/a = 2.6621 in real
h-BN-layered crystals c/a = 2.6602.
Fullerites and Fullerides
Consideration of B12N12, B24N24, and B60N60 molecules as ana-
logs of carbon fullerenes allows to predict [27,232,239,240]
the existence of inorganic polymeric chains and at least 10
boron nitride fullerite crystals and calculate their lattice
parameters and density. It has been constructed that a num-
ber of small clusters BnNn (with n = 12, 16, 18, 24, 34, 60)
are able to form zeolite-like covalence crystals. The com-
parison between these structural calculations and available
93
experimental data allows identifying the fullerite with simple
cubic symmetry constructed from B12N12 molecules with BN
intermediate explosive phase.
Using DFT calculations, it was predicted [241] that single-
walled hemispherical-caped boron nitride BN nanotubes with
small diameters can be produced via the coalescence of stable
nanoclusters. Specifically, the assembly of BnNn (n = 12, 24)
clusters exhibiting particularly high stability and leading to
armchair (3,3) and (4,4) BN nanotubes, respectively, was
considered.
Maps of the distribution of electron density in the boron
nitride fullerite with diamond-like structure having the B12N12
molecules at the vertices have been calculated [167] using an
ab initio full potential augmented plane wave method.
Considering the problem how BN fullerenes could be
assembled in molecular solids, the work [242] was focused on
the smallest synthesized BN fullerene, B12N12, which is built
by squares and hexagons. First, the interaction between two of
these fullerenes was analyzed, using the hybrid density func-
tional methods. Two different interactions have been studied
in the dimer, a square facing a square (S–S) and a hexagon
facing a hexagon (H–H). In both cases, B is facing N. The
most stable dimer was found to be S–S facing, with covalent
interactions between the monomers, but other dimers with
weak interactions have been found as well, which opens possi-
bilities of new systems, as in the case of fullerene dimers and
solids. The solids resulting from the infinite repetition of the
characterized dimers were optimized, finding two different
solids, with covalent and weak interactions between mono-
mers, respectively.
Molecular and solid forms of BN, based on stoichiomet-
ric and nonstoichiometric fullerenes, were predicted in Ref.
[243] by means of ab initio calculations. The study of the
energetics of dimer formation indicated that the reactivity
of BN fullerenes depends strongly on the stoichiometry.
The stoichiometric fullerenes form strong covalence bonds
between the tips of neighboring cages, while the tips of
nitrogen-rich fullerenes “repeal” each other. Calculations
predict the large interstitial channels, with diameters of
5–8  Å, but the hardness comparable to that of hard met-
als. In contrast, nitrogen-rich units (with the exception of
B12N16) should form loosely bound molecular solids (like the
standard carbon fullerenes). The following values of binding
energy per intermolecular bond were predicted: B12N16 and
B16N16 dimers 0.47 and 0.45 and B12N16, B16N16, and B36N36
fullerite crystals 0.34, 0.30, and 0.29 eV. In contrast to this,
nitrogen-rich cells of boron nitride (except B12N16) are to be
associated with weakly bound molecular solids like conven-
tional carbon fullerenes.
As for BN polymorphic modification with diamond-like
structure and B12N12 molecules instead atomic sites [244],
structure of which earlier called by E-phase, it was named
[27] as “hyperdiamond”. The experimental value for its lattice
parameter, 11.14 Å, is in good agreement with the predicted
one, 11.52 Å.
First-principle methods were applied [130] for calcula-
tions of new cluster and crystalline nanophases of refractory