J. Phys. Chem.

B 2008, 112, 10217–10220 10217

Thermodynamic Stability of Novel Boron Sheet Configurations

Kah Chun Lau*,† and Ravindra Pandey*,‡

Department of Chemistry, George Washington UniVersity, Washington, District of Columbia 20052, and
Department of Physics, Michigan Technological UniVersity, Houghton, Michigan 49931
ReceiVed: April 16, 2008

Thermodynamic stability together with the vibrational spectrum of several structural motifs of the pristine
2D boron sheet are investigated. The results suggest that the nature of the chemical bonding, rather than
thermal effects, appears to be the prime factor in determining the stability of atomic monolayers of boron.
The most stable configuration is predicted to be composed of a hybrid of triangular and hexagonal configuration.
A boron sheet composed of either perfect triangular or perfect hexagonal motifs is unlikely to be synthesized.
The distinctive features predicted in vibrational and thermodynamic properties for boron sheet configurations
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are expected to exhibit their signatures in the corresponding pristine nanotubes and crystalline bundles.
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I. Introduction successfully the structural parameters of the boron crystalline

solid, R-B12. For example, the calculated lattice constant is 4.99
The stability of two-dimensional (2D) structures is known
Å as compared to the GGA value of 5.05 Å15 and experimental
to be the long-standing challenging research problem in the field
value of 5.06 Å.18,19
of materials science. It is well-known that the long-wavelength
To simulate a 2D boron sheet, a supercell was constructed
thermal fluctuations can destroy the long-range order of a 2D
by placing a basic unit in the xy-plane inside a rectangular grid
lattice.1 It therefore remains questionable, in principle, whether
with a surface-to-surface separation of ∼15 Å in the z-direction.
a free-standing 2D atomic layer could exist.1–6 In recent years,
The sheet configuration was built by repeating the basic unit
graphene, a single layer of carbon atoms densely packed in a
consisting of six to eight boron atoms depending on a given
honeycomb crystal lattice, has sparked much scientific interest.6–9
configuration. Calculations were deemed converged when
Owing to its superior form in the quasi one-dimensional (1D)
changes in total energy were less than 10-5 eV and those in the
structure when rolled up to form a nanotube,10 fundamental
interatomic forces were less than 0.01 eV/Å. The optimized
understanding of novel 2D sheet configurations becomes an
sheet configurations were then used to calculate the frequencies
important supplement to predict the properties of the corre-
with the convergence criterion of 10-6 eV and 10-4 eV/Å for
sponding tubular configurations.
total energy and interatomic forces, respectively.
Several theoretical studies have focused on the 2D boron
The vibrational free energy is calculated within the harmonic
sheet11–16 as a precursory step to form boron nanostructures.
approximation using the direct method.17 This method employs
These studies have, however, reported only the structural and
the forces on the atoms induced by the displacements of other
electronic properties without looking into the question of their
atoms in the supercell. The calculated forces are used to obtain
stability at ambient conditions. This is what we propose to do
elements of the dynamic matrix related to the interatomic force
in this article: perform a detailed analysis of the thermodynamic
constants. The vibrational frequencies are then obtained via the
stability of boron sheets. Specifically, we will focus on first
diagonalization of the dynamic matrix in which the atomic
principles calculations of the vibrational frequency, free energy,
displacements may correspond to a particular phonon mode. If
and heat capacity of several sheet configurations, and we will
frequency of a particular mode is imaginary, the configuration
compare the results with those obtained for the well-studied
is said to be not stable, indicating it to be in a transition state,
graphene to gain insight in the stability of the 2D boron sheet
instead of representing a local minimum on the energy surface.
configurations.
III. Results and Discussion
II. Methodology
Figure 1 displays the configurations of R-sheet, β-sheet, flat
Electronic structure calculations were performed within the and buckled triangular sheets, and flat and distorted hexagonal
local density approximation (LDA) to density functional theory sheets considered in this work. The relative energy differences
(DFT). A plane wave basis set was used with a cutoff of 430 (Table 1) among the sheet configurations are consistent with
eV, and the valence-core interaction was described by the the reported values in the previous studies.11–16 The cohesive
projector augmented wave potential as implemented in the energy (or binding energy) of the sheet configurations is
Vienna ab initio simulation package (VASP).17 The 23 × 23 × predicted to be less than that of the boron rhombohedral solid.
1 Monkhorst-Pack grid was used, and the k-space integrations The binding energy of the most stable R-sheet is ∼93% of the
were carried out using the Gaussian smearing width of 0.1 eV. R-B12 solid.
We note that the model parameters employed reproduced A. Stability. First, we performed calculations on the hex-
agonal graphene sheet to set the benchmark for comparison with
* Corresponding authors. K.C.L. e-mail: kah.lau.ctr.my@nrl.navy.mil. the results obtained for the boron sheet configurations. For
R.P. e-mail: pandey@mtu.edu.
† George Washington University. graphene, the frequencies spanning from 383 to 1598 cm-1 are
‡ Michigan Technological University. found to be consistent with the previously reported values.20
10.1021/jp8052357 CCC: $40.75  2008 American Chemical Society
Published on Web 07/29/2008
10218 J. Phys. Chem. B, Vol. 112, No. 33, 2008 Lau and Pandey

Figure 2. Vibrational frequency spectrum (in cm-1) of the boron sheet

configurations.

In the previous study of the hexagonal boron sheet,15 we

predicted that the induced distortions, breaking the D6h sym-
metry of the hexagonal lattice to a lower D2h symmetry of the
orthorhombic lattice, make the sheet configuration relatively
stable. The present calculations further confirm the stability of
the distorted hexagonal sheet where no imaginary frequencies
were found. At Γ, the eigenvalue distribution is relatively more
dispersive than the perfect hexagonal sheet as shown in Figure
2. The highest vibrational mode at 1401 cm-1 is associated with
the symmetric stretching of the σ-bond with the bond distance
of 1.62 Å. It is slightly smaller than that in graphene (∼1598
cm-1), thereby exhibiting similar strength of σ bonds present
in the distorted hexagonal boron sheet and graphene.
We now consider the configurations based on the triangular
Figure 1. Two-dimensional sheet configurations of boron: (top) R-sheet networks which resemble the icosahedral B12 networks of the
and β-sheet, (center) buckled triangular and distorted hexagonal, and elemental boron solids (Figure 1). In the perfect triangular boron
(bottom) perfect triangular and perfect hexagonal configurations.
sheet, both the high atomic coordination and the electronic-
TABLE 1: Binding Energy (Eb) and Structural Parameters deficient character of boron yield a nearly homogeneous electron
(Bond Length (d) and Buckling Height (∆z)) of Sheet density distribution in the 2D lattice.15 Its Fermi level is high
Configurations enough to force some of the electrons to occupy antibonding
structural parameters molecular orbitals which, in turn, induce a destabilizing effect
in the 2D lattice making it to be highly chemically reactive.16
sheet configuration Eb d (Å) ∆z (Å) The calculated frequency spectrum with several imaginary
R-sheet 6.74 1.66-1.69 - modes also show the flat triangular sheet to be highly unstable.
β-sheet 6.71 1.63-1.74 - In particular, all of its transverse out-of-plane and ZA bending
buckled triangular sheet 6.64 1.61, 1.83 0.84 modes are not stable with imaginary νc ranging from 261 to
perfect triangular sheet 6.46 1.69 -
193 cm-1. It therefore appears that that the three-center bonds
distorted hexagonal sheet 6.44 1.62, 1.65 -
perfect hexagonal sheet 5.72 1.67 - present in the perfect triangular lattice are not strong enough to
bind the boron atoms in a 2D lattice.
The results find that the buckling (∆z ) 0.84 Å, Table 1)
The highest vibration mode, ν ∼ 1598 cm-1 is associated with removes the instability of a perfect triangular boron sheet.12–15
the symmetric stretching mode of the strong σ-bond. The out- The symmetry-reducing distortions lead to the formation of the
of-plane transverse polarization in the optical mode (i.e., ZO at σ-bonds with an increase in the stability by 0.18 eV/atom in
Γ) emerges at ∼896 cm-1 consisting of in-phase and antiphase the buckled sheet. The presence of σ-bonds with Rσ ) 1.61 Å
out-of-plane atomic oscillations. In the low-frequency regime is well-represented by the atomic oscillations having stretching
(i.e., ∼383-685 cm-1), the modes are related to either transverse modes in the range of 1284-1348 cm-1 (Figure 2). For
out-of-plane or bending modes of atomic oscillations in the 2D frequencies in the range of 541-741 cm-1, oscillations are
lattice. dominated by the symmetric and asymmetric of the diagonal
For the hexagonal boron sheet, the calculated results find bonds with Rdiag ) 1.83 Å (Figure 1, Table 1). The long-
several imaginary frequencies, thus confirming its instability. wavelength modes (214-439 cm-1) are associated with the out-
The largest imaginary frequency of about νc ∼ 531 cm-1 shows of-plane atomic oscillations. In general, the results confirm that
the instability of its in-plane symmetric stretching mode of the distortions induced in a perfect 2D lattice (e.g., hexagonal or
σ-bond. Similarly, the out-of-plane ZA bending modes are also triangular) yield stable configurations.
associated with the imaginary frequencies. The results therefore The vibrational spectrum of the energetically stable R- and
conclusively rule out the existence of the pristine hexagonal β-sheet configurations, composed of triangular and hexagonal
boron sheet at ambient conditions. motifs, shows features of the isolated triangular and hexagonal
Thermodynamic Stability of Boron Sheet
Figure 3. Thermodynamic stability of the boron sheets (BS) in terms
of the calculated Helmholtz free energy. The dotted lines are the
computed free energy including zero-point vibration energy as stated
in eq 1.
sheet configurations (Figure 2). In the spectrum ranging from
128 to 1146 cm-1, the highest mode is the symmetric stretching
mode associated with three-center bonds in the 2D lattice. This
is a signature of the triangular motif (Figure 2). The next highest
mode exhibits an asymmetric stretching along the edges of
hexagonal hole (Figure 1), resembling the one predicted for the
hexagonal sheet at about ∼910 cm-1. The long-wavelength
oscillations in the range of 128-283 cm-1 are associated with
the out-of-plane oscillation and bending modes.
In general, the ZA bending modes are predicted to be lower
in energy relative to those in graphene. The long-range ordering
in the boron sheet is, therefore, likely to be more vulnerable to
the long-wavelength thermal fluctuations as compared to
graphene, though the sheet configurations of boron and graphene
are thermodynamically feasible.
B. Thermodynamic Properties. From the computed phonon
spectrum of the sheet configurations, the temperature-dependent
vibrational Helmholtz free energy and entropy can be calculated
in the harmonic approximation.21
F(V, T), the free energy of a crystal, can be written as a sum
of E(V), the energy of the static lattice at the equilibrium
configuration, and Fvib(V, T), the vibrational free energy associ-
ated with the modes, ω(q).
F ) E + Fvib ) E + ∑ pω(q)
2
- ST (1)
q
Here, S is entropy, ∑q pω(q)/2 is the summation of contributions
of the zero-point energy from each phonon mode, and T is the
temperature.
Considering the first-order corrections to be small, S can be
calculated20 as follows:
S ) -kB ∑ ln(1 - e-pω(q)/k T)
B
(2)
q
Figure 3 shows the variation of the total free energy with
temperature for the configurations considered. The order of the
stability remains nearly the same as predicted from energies
calculated at zero temperature; R-sheet being the most stable.
Thus, the results suggest that the nature of the chemical bonding
rather than the thermal effects determines the relative stability
of the 2D boron lattice. We note that contributions from the
vibrational term do affect the ordering of the stability of the
distorted hexagonal and flat triangular boron sheet. The distorted
hexagonal sheet becomes relatively more stable at about 350 K
relative to the flat triangular sheet.
J. Phys. Chem. B, Vol. 112, No. 33, 2008 10219
Figure 4. Calculated constant volume heat capacity (in J K-1 mol-1)
vs temperature plots of boron sheets and graphene. The black solid
lines are as follows: (cross) graphene, (diamond) R, (star) buckled
triangular, (triangle) distorted hexagonal, (square) perfect triangular,
and (circle) hexagonal boron sheets. The red dotted horizontal asymptote
is the Cv ) 3R (where R is the gas constant) value, governed by the
Dulong-Petit law.
The lattice heat capacity per unit cell at constant volume can
be defined as follows:
( ) ( )
∑ cv(q) ) kB∑ 1
pω(q) 2
CV(T) ) (3)
2kBT 2 pω(q)
q q sinh
2kBT
In order to compare the results of boron sheets with carbon
graphene, the normalized heat capacity CV (i.e., J K-1 mol-1)
is computed. In the high-temperature regime, as shown in Figure
4, CV is bound by the asymptote stated by the Dulong-Petit
law, CV ) 3R. In the low-temperature regime, CV of the boron
sheets is different from that of graphene. Note that CV of the
thermodynamic stable boron sheets (i.e., R, buckled triangular
and distorted hexagonal) is generally larger than that of
graphene. The heat capacity values of R, buckled triangular,
and distorted hexagonal sheets are nearly identical at high
temperatures. It is a manifestation of the law of corresponding
states for different materials with essentially very similar Debye
temperatures.20
IV. Conclusions
In summary, first-principles calculations based on density
functional theory are performed to calculate the thermodynamic
properties of the several configurations of the pristine 2D boron
sheet. The results suggest that a boron sheet composed of either
perfect triangular or perfect hexagonal motifs is unlikely to be
synthesized. The induced distortions in either a perfect hex-
agonal or triangular sheet configuration are found to provide
the stability of the 2D lattice. The thermodynamic stable
configurations are predicted to be composed of a hybrid of
triangular and hexagonal configurations and the buckled trian-
gular and the distorted hexagonal sheets. It is expected that
distinctive features predicted in vibrational and thermodynamic
properties for sheet configurations will exhibit their signatures
in the corresponding pristine nanotubes and bundles of boron.
Finally, the results find that the nature of chemical bonding,
not the thermal effects, is the prime factor in determining the
stability of boron sheet configurations.
Acknowledgment. The work at Michigan Technological
University was supported by DARPA (contract number ARL-
10220 J. Phys. Chem. B, Vol. 112, No. 33, 2008
DAAD17-03-C-0115). We thank Prof. M. A. Blanco, S.
Gowtham, Haiying He, and Prof. R. Orlando for helpful
comments during this work.
References and Notes
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