Letter

pubs.acs.org/JPCL

Ab Initio Study of the Dielectric and Electronic Properties of

Multilayer GaS Films
Yan Li,* Hui Chen, Le Huang, and Jingbo Li*
State Key Laboratory of Superlattice and Microstructures, Institute of Semiconductors, Chinese Academy of Sciences, No. A 35,
Qinghua East Road, Haidian District, Beijing 100083, China

ABSTRACT: The dielectric properties of multilayer GaS films have been

investigated using a Berry phase method and a density functional
perturbation theory approach. A linear relationship has been observed
between the number of GaS layers and slab polarizability, which can be
easily converged at a small supercell size and has a weak correlation with
different stacking orders. Moreover, the intercoupling effect of the stacking
pattern and applied vertical field on the electronic properties of GaS bilayers
has been discussed. The band gaps of different stacking orders show various
downward trends with the increasing field, which is interpreted as giant
Stark effect. Our study demonstrates that the slab polarizability as the
substitution of conventional dielectric constant can act as an independent
and reliable parameter to elucidate the dielectric properties of low-
dimensional systems and that the applied electric field is an effective method
to modulate the electric properties of nanostructures.

GaS, a new class of layered materials with honeycomb
structures, has raised increasing scientific and engineering
interest due to a wide range of fascinating physical and chemical
properties associated with its low-dimensional forms. Similar to
graphite, GaS is formed by strong in-plane covalent bond and
weak out-of-plane van der Waals forces, which enables the
micromechanical cleavage into two-dimensional nanosheets.
Recently, the preparation, isolation and rapid unambiguous
characterization of large sized ultrathin layers of GaS have been
reported by Late etc.1 Then, the same group has successfully
fabricated the single-sheet-based field-effect transistors (FETs)
of GaS and GaSe with typical n-type and p-type conductance,
respectively.2 According to their results, good ON/OFF current
ratios ranging from 104 to 105 and differential mobilities of 0.1
and 0.6 cm2 V−1 s−1 have been achieved for single-sheet GaS
and GaSe FET, respectively. In addition, high photo-
responsivity of ultrathin GaS nanosheet to the UV−visible
wavelength has been demonstrated on both SiO2/Si and
polyethylene terephthalate (PET) substrates.3 What is more
exciting is that GaS nanosheets are found to exhibit strong and
distinct photoresponsivity performances in different gas
environment.4 On the theoretical side, single-layer GaS has
been demonstrated to be suitable as a photocatalyst for water
splitting,5 and the band gap can be tuned by mechanical strains
for a better match with the solar spectrum, thereby increasing
the efficiency of solar energy conversion.6 Therefore, the
versatile properties of GaS nanosheets suggest that this new
kind of 2D material provides great possibilities for the
improvement in the performance of transistor, photodetector,
gas sensor, and energy engineering.
We explore the dielectric properties of multilayer GaS films
using a Berry phase approach within density functional theory
(DFT) under the application of finite electric field.7 The results
are validated with density functional perturbation theory
(DFPT) approach, which addresses the response of an
inhomogeneous electron gas to external perturbation.8,9 We
calculate the slab polarizability of different GaS nanosheets with
three different vacuum spaces to test the reliability of this
parameter and use it to predict the dielectric constant of bulk
GaS in the perpendicular direction. In addition, we systemati-
cally investigate the effect of vertical electric field on the
electronic properties of various bilayer GaS configurations and
examine the charge distribution induced by the field. The
physical mechanism is discussed in detail, and relevant
coefficients are predicted.
The bulk GaS crystallizes in the β phase with space group
P63/mmc and Bernal stacking, while its monolayer counterpart
in the form of S−Ga−Ga−S sheet exhibits honeycomb
structure with space group P6̅ m2, as illustrated in Figure 1a.
The optimized crystal constants a and c are equal to 3.573 and
15.511 Å, respectively, and the bond lengths for Ga−Ga bond
and Ga−S bond are 2.436 and 2.336 Å, respectively. All of these
calculated structure parameters are in good agreement with
previous works.1,4−6,10−12
To have a thorough knowledge of 2D GaS, we also examine
the electronic properties of few-layer GaS nanosheets and find
that the band gaps decrease monotonously with the increasing
number of layers. The band structures of the bulk and single-
layer GaS are illustrated in Figure 1c. It is worth noting from
Received: January 21, 2015
Accepted: March 9, 2015
Published: March 9, 2015

© 2015 American Chemical Society 1059 DOI: 10.1021/acs.jpclett.5b00139

J. Phys. Chem. Lett. 2015, 6, 1059−1064
The Journal of Physical Chemistry Letters
Figure 1. (a) Top and side views of bulk GaS. The rhombic shadow
presents the unit cell of GaS. (b) Band gaps and energy difference
(ΔE) between VBM and Γ point as a function of number of layers.
The inset is the Brillouin zone of GaS. (c) Band structures of the bulk
and monolayer GaS.
the band structures that the band inversion occurs with the
dimensionality change. More specifically, when the dimension-
ality decreases from three to two, the valence band maximum
(VBM) shifts horizontally from Γ point to two symmetric
points nearby, thereby forming the inverted Mexican hat shape,
while the conduction band minimum (CBM) remains
unchanged at M point. The energy difference between the
VBM and Γ point also exhibits a decreasing tendency with the
increasing number of layers, and the double peaks disappear
when the thickness reaches five, which can be seen in Figure 1b.
On the basis of the projection analysis, it is found that the
electronic states near the Fermi level are contributed mainly by
S p and Ga s,p levels. At the Γ point, the occupied band are
dominated by the S pz and Ga s,pz states. While at the two
symmetric peaks near the Γ point, there is also appreciable py
character. These states near the Fermi level are delocalized and
have an antibonding attribute. On increasing the distance
between consecutive GaS layers, the antibonding states are
pushed down by the decreasing interlayer interaction. The
states at the Γ point only having pz character are much more
affected than the two peaks near the Γ point having mixed py
and pz states; therefore, the energy level at the Γ point descends
more quickly than that of at the two peaks nearby, finally
forming the inverted Mexican hat shape.
Next, we turn to the dielectric properties of 2D GaS systems
to fully explore the application potential of 2D GaS nanosheets.
The macroscopic dielectric tensor of an insulating system is
defined as13
∂Pi
εij = δij + 4π
∂Ej
(1)
where P is the macroscopic polarization, E is the applied finite
homogeneous electric field, and i and j are Cartesian
coordinates. Here we apply electric field perpendicular to the
GaS planes ranging from −0.01 to 0.01 V/Å with an increment
of 0.005 V/Å to study the dielectric properties along the c axial.
The code will first determine the zero-field ground state of an
insulating system and the macroscopic electric polarization
through the evaluation of the Berry phase expressions following
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the modern theory of polarization,14−17 then compute the field-
polarized ground-state orbitals. Additionally, the change in the
macroscopic electric polarization is estimated under the
application of a finite homogeneous electric field. P = χE is
generally used to define the system polarization, where χ is the
electric susceptibility, which can be obtained from the gradient
of the polarization versus electric field for each system.
Therefore, the system dielectric constant can be expressed as
ε = 1 + 4πχ (2)
As the plane-wave density functional and pseudopotential
methods implemented in the code rely on a supercell geometry,
which is composed of periodically repeated molecules or slabs,
the convergence of calculated properties must be checked
against the increase in the size of the vacuum region, which is
extremely crucial for the study of dielectric properties. This is
because of the long-range of electrostatic interactions and the
possible spurious electric field contributed by the periodic
boundary conditions.
For the supercell dimension perpendicular to the GaS plane,
we did the total energy convergence and dielectric constant
values tests with three different vacuum spaces; these are 15, 20,
and 30 Å. The results show that 15 Å is large enough to provide
an energy difference <1 meV per atom between the total energy
for 20 and 30 Å. However, it is found that the dielectric
constant values strongly depend on supercell size, a fact that has
also been reported for other low-dimensional systems by some
literatures.7,9,18 Figure 2 shows the dielectric constant value as a
Figure 2. Dielectric constant of GaS nanosheets as a function of the
number of layers.
function of number of layers. For GaS nanosheets with the
same vacuum space, the dielectric constant values exhibit a
nearly linear relationship with the number of layers, while they
decrease with the increasing supercell size for the same number
of layers. In this respect, the effect of adding GaS layers on the
polarization and the dielectric properties in 2D systems cannot
be precisely described by the conventional dielectric constant,
which is commonly used for insulating bulk materials. In all
cases, the dielectric constant values calculated by the Berry
phase method and DFPT approach coincide very well with the
error magnitude within 1%.
To solve the predicament, it is more reasonable to adopt the
polarizability, α, which generally defines the relationship
between the induced dipole moment, pi, of an atom and the
electric field, Eloc,j, that generates this dipole moment, namely
pi = ∑ αijE loc, j
j (3)
DOI: 10.1021/acs.jpclett.5b00139
J. Phys. Chem. Lett. 2015, 6, 1059−1064
The Journal of Physical Chemistry Letters Letter

For 2D systems, the polarizability, α, of a slab can be defined in

the form of
m = αE loc /S (4)
where m is the dipole moment per unit surface area, Eloc is the
electric field vertical to the slab, and S is the surface area of GaS
nanosheets. The Eloc is estimated as19,20
4πm
E loc = E +
L (5)
where L is the supercell length along the c axial. From eqs 2, 4,
and 5, we get the polarizability of the isolated slab as
Ω ⎛⎜ ε − 1 ⎞⎟
α= Figure 3. Slab polarization as a function of the number of layers.
4π ⎝ ε ⎠ (6)
where Ω is the supercell volume. extra tests with that of 20 and 30 Å present very similar results.
On the basis of eq 6, the polarizability of GaS nanosheets We can expect that the linear increase in the slab polarizability
with different vacuum spaces is listed in Table 1. It is found that with the increase in layers could also be found in other 2D
systems, such as transition-metal dichalcogenides, h-BN.
Table 1. Slab Polarizability of Different GaS Nanosheets As a Because the stacking orders of GaS monolayers can vary
Function of Vacuum Spaces during different experimental conditions, we are also curious
about whether the stacking configurations have an influence on
number of
layers 1 2 3 4 5 6
the slab polarizability of the few-layer GaS films. Here we take
the GaS bilayer as an example to investigate the relationship
15 Å 5.65 11.08 16.64 22.18 27.74 33.28
between the slab polarizability and the stacking patterns. We
α 20 Å 5.65 11.13 16.67 22.19 27.74 33.29
construct five typical configurations and name them by the
30 Å 5.66 11.16 16.68 22.19 27.77 33.31
notation illustrated in Figure 4. In I- and II-GaS configurations

the slab polarizability can be converged at 15 Å, which indicates

that this parameter is independent of the vacuum space when
the distance between the periodic GaS stacks is sufficient to
prevent electrostatic interactions between periodic images. It is
also noted that the slab polarizability increases with the
increasing number of layers, which exhibits the same change
with respect to the variation of the dielectric constant. The slab
polarizability can be viewed as the effective volume of the slab
that acts as a metal under the vertical electric field. According to
eq 6, there are two extreme points for the slab polarizability:
One is ε = 1, α = 0, which represents a slab of vacuum space;
another one is ε = ∞, α = Ω/4π, which represents the metal
case. Therefore, the increase in the number of layers means the
linear increase in the effective metallic volume polarized by the
field.
According to refs 7, 9, and 21, the slab polarizability of an
isolated N layers can also be expressed as
Ω B ⎛ εB − 1⎞
αN = N ⎜ ⎟ + 2αS
8π ⎝ εB ⎠ (7)
where εB and ΩB are the dielectric constant and volume of the
bulk unit cell, respectively, N is the number of GaS layers, and
αS is the surface polarizability, which measures the difference Figure 4. Top and side views of five different GaS stackings, which are
dubbed as I-, II-, III-, IV, and V-GaS.
between the dielectric properties of the bulk and of the slab.9 It
can be seen from eq 7 that the slope depends only on the bulk
dielectric constant. As illustrated in Figure 3, by fitting a linear (Figure 4a,b), two monolayers are stacked with the top-layer
relationship between the slab polarizability and the number of atoms superimposed on the bottom-layer atoms. Their
layers, we extract the vertical dielectric constant of the bulk GaS difference is that in the I-GaS case, one type of atom is
as 5.29, which is extremely close to the dielectric constant superimposed on the other type, with the same stacking in bulk
values 5.34 and 5.35 calculated by the Berry phase method and GaS, while in II-GaS case, the same type of atoms are
DFPT approach, respectively. The term of the surface superimposed. In III-GaS configuration, the S atoms of both
polarizability is 0.0585, which indicates that the surfaces are monolayers are superimposed on each other, while the Ga
less polarizable than the bulk. The data used in Figure 3 are atoms of the top monolayer are located above the hexagon
based on the calculations with a vacuum space of 15 Å, and centers formed by S atoms of the bottom monolayer; in IV-GaS
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configuration, the Ga atoms of both layers are superimposed on
each other, while the S atoms of the top monolayer are situated
above the hexagon centers formed by Ga atoms of the bottom
layer; in V-GaS configuration, the Ga atoms of the top
monolayer are superimposed on the S atoms of the bottom
layer, and the S atoms of the top monolayer are above the
hexagon centers formed by Ga atoms of the bottom monolayer.
Also, both the Berry phase DFT method and DFPT approach
have been applied in the calculations. The calculated slab
polarizability together with other basic physical properties of
the GaS bilayers of different stacking orders is listed in Table 2,
Table 2. Physical Properties of GaS Bilayer with Different
Stackings: Interlayer Distances (d), Slab Polarization (α),
Relative Energies (ΔE) and Binding Energies (Eb) Relative
to the GaS Monolayer, and Band Gaps (Eg)
stacking I II III IV V
d (Å) 7.76 8.41 8.38 7.75 7.75
α 11.08 11.13 11.14 11.09 11.09
ΔE (meV) 0 48.50 48.36 3.38 0.59
Eb (meV) 147.59 99.09 99.23 144.21 147.00
Eg (eV) 2.13 2.30 2.29 2.16 2.14
according to which the bilayer configurations can be divided
into two categories in light of interlayer distances. The first has
much larger interlayer distances, including II-GaS (8.41 Å) and
III-GaS (8.38 Å); the second has smaller interlayer distances,
including I-GaS (7.76 Å), IV-GaS (7.75 Å), and V-GaS (7.75
Å). In the GaS monolayer, there is charge transfer from Ga
atoms to S atoms due to the stronger electronegativity of S
atoms than that of Ga atoms. The calculated charge transfer
from Ga atom to S atom is 0.87 electron per Ga−S pair in GaS
monolayer by the Bader analysis.27 In this respect, the GaS
monolayer can be considered as a sheet composed of equal
numbers of Ga2+ and S2− ions, and the Ga2+ and Ga2+ (S2− and
S2−) ions are repulsive and the Ga2+ and S2− are attractive
because of the Coulomb interaction. Furthermore, the electrons
transferred from Ga atoms to S atoms occupy the pz orbitals of
S atoms and deplete the pz orbitals of Ga atoms. Given that the
S atoms of the top monolayer locate directly above the S atoms
of the bottom monolayer, the pz electrons in different layers
will repel strongly with each other. Therefore, the equilibrium
interlayer distances are relatively larger in II- and III-GaS cases
than the other three cases, while the binding energies are much
smaller for II- and III-GaS bilayers, which also indicates that the
I-, IV, and V-GaS bilayers are more stable than II- and III-GaS
bilayers. The slab polarizability values of the five configurations
also fall into the two categories but show slight differences,
which suggests that the slab polarizability has a very weak
relationship with the stacking patterns.
The discovery that applied electric field can open up and
modulate the band gap of bilayer graphene22−26 has intrigued
great interest in the effect of electric field on other 2D systems,
and for industrial applications, it is important to explore the
electronic properties of these 2D systems under applied field as
electronic devices. In this work, we investigate the effect of
applied electric field on the electronic properties of GaS
bilayers with five various stacking orders. The external electric
field ranging from −10 to 10 V/nm is applied perpendicular to
the plane of all five configurations. As the applied electric field
breaks the inversion symmetry of the bilayer structures, we turn
off the symmetry in all calculations with applied electric field.
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The positive direction of electric field is set from the bottom
monolayer to the top monolayer. The band gaps as functions of
the external electric field are illustrated in Figure 5. The
Figure 5. Band gaps as a function of the applied field for five GaS
bilayer configurations.
symmetrical distribution of the band gaps on both sides of zero
electric field suggests that the positive and negative electric
fields have the same effect for all five cases in modulation of
their band structures. It is found that the band gaps of all five
cases decrease approximately linearly in a large range with the
increasing electric field, even though the initial response of the
band gap to the applied field is nonlinear, likely quadratic.
Other theoretical studies on boron nitride nanoribbons,28−30
nitride bilayers,31 and some transition-metal dichalcogenides
bilayers32 have also shown that the electric fields can
significantly reduce the band gaps and even render them
metallic in some instances. By analogy to the atomic Stark
effect, researchers dubbed this phenomenon the giant Stark
effect (GSE). Enlightened by these preceding studies, we fit the
approximate linear relationship between the band gaps and the
applied electric field, and the slope of the curve can be
described as
dEg
= −eS
dE (8)
where e is the electron charge and S is the linear GSE
coefficient. We also predict the critical field, Et, for the
semiconductor−metal transition in five different bilayer
stackings. The fitted S and predicted Et are listed in Table 3.
Table 3. Fitted Slopes, S, of the Band Gap versus the Applied
Electric Field and the Predicted Critical Fields, Et, for the
Semiconductor−Metal Transition in GaS Bilayers with
Different Stackings
stacking I II III IV V
S 0.106 0.166 0.161 0.110 0.107
Et (V/nm) 20.16 13.87 10.18 19.61 19.94
It is apparent that the II- and III-GaS bilayers show a faster rate
than those of the other three cases, which means that the
vertical electric field has a stronger ability to modulate the band
gaps of II- and III-GaS cases than to those of the other three
cases, while the critical values for the semiconductor−metal
transition of I-, IV-, and V-GaS bilayers are much larger than
those of II- and III-GaS bilayers.
DOI: 10.1021/acs.jpclett.5b00139
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The Journal of Physical Chemistry Letters
To attain more insight into the field-induced variation of the
electronic properties of these bilayer GaS systems, we perform
more detailed electronic structure analyses and take I-GaS as a
representative for brevity, which is sufficient to illustrate the
similar variation trend found in other cases. The band
structures of I-GaS under the external electric fields of 0, 5,
and 10 V/nm are illustrated in Figure 6. Their respective
Figure 6. Band structures of I-GaS bilayer under the external field of 0,
5, and 10 V/nm.
highest electron occupation energies are set as zero. It is found
that the VBM remains symmetrical near the Γ point, while the
CBM finally moves from M point to Γ point. The applied
electric field not only affects the band alignments of the bilayer
systems but also brings about the charge redistribution for the
bilayers. The charges at VBM and CBM points are initially
distributed over both layers but are mostly localized at the
bottom monolayer and top monolayer under the applied
electric field of 9 V/nm, respectively, as clearly seen in Figure 7.
Figure 7. Charge density distribution of the VBM and CBM of I-GaS
under the external electric fields of (a) 0 and (b) 9 V/nm. All
isosurfaces are set at 0.005 e/Å3.
The essential changes of the electronic properties under applied
electric field hold true for all five bilayer cases, with only slight
difference in band gaps and variation rates.
In summary, we have investigated the dielectric properties of
few-layer GaS films by both a Berry phase method and a DFPT
approach using first-principles calculations. The slab polar-
izability of few-layer GaS nanosheets has been determined and
exhibits a linear relationship with the number of GaS layers.
Independent of the supercell size and the stacking order, slab
polarizability has been demonstrated to be an effective and
meaningful parameter to describe the dielectric properties of
low-dimensional systems. Additionally, the bulk dielectric
constant extracted from the linear relationship is 5.29, which
is in good agreement with the values calculated by the Berry
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phase method (5.34) and DFPT approach (5.35). We have also
explored the physical properties of five GaS bilayer
configurations. The binding energies and band gaps vary with
different interlayer distances depending on different stacking
patterns. It is found that an applied electric field can
significantly reduce the band gaps of the bilayer configurations,
although it appears that rather large fields would be required to
induce a complete semiconductor−metal transition. The
relationship between band gap values and applied electric
field can be elucidated by GSE. The effect coefficient, S, and
critical field are also characterized by different stacking patterns.
We hope our calculated results of the dielectric and electronic
parameters of few-layer GaS nanosheets can expand the known
space of layered materials and provide theoretical basis and
inspiration for future experiments.
For our research, we performed first-principles calculations
using the Vienna ab initio simulation package (VASP),33 which
is based on the DFT in a plane-wave basis set with the
projector-augmented wave (PAW) method.34 The generalized
gradient approximation of Perdew−Burke−Ernzerhof (GGA-
PBE)35 including van der Waals corrections proposed by
Grimme36 was chosen for the exchange-correlation functional.
Energy cutoff for plane-wave expansion was set to 500 eV. A
large vacuum space of >15 Å was added to all 2D nanosheets to
prevent the interaction between adjacent images. Brillouin zone
sampling was performed with Monkhorst Pack (MP) special k-
points meshes.37 k-point grids of 16 × 16 × 6 and 16 × 16 × 1
were chosen for the calculations of the bulk and 2D GaS
systems, respectively. All of the structures were fully relaxed
using the conjugated gradient method until the Hellmann−
Feynman force on each atom was <1 meV/Å.
■
AUTHOR INFORMATION
Corresponding Authors
*Y.L.: E-mail: bclly2008@semi.ac.cn.
*J.L.: E-mail: jbli@semi.ac.cn.
Author Contributions
Y.L. and H.C. worked on the electronic structure calculations
and wrote the manuscript. Y.L. performed the dielectric
calculations. All authors analyzed the data and discussed the
results. Y.L. and H.C. contributed equally. All of the authors
read and commented on the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China under grant no. 91233120 and the
National Basic Research Program of China (2011CB921901).
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1064 DOI: 10.1021/acs.jpclett.5b00139

J. Phys. Chem. Lett. 2015, 6, 1059−1064