ARTICLE IN PRESS

Physica B 405 (2010) 3501–3506

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Physica B
journal homepage: www.elsevier.com/locate/physb

First-principles calculations on third-order elastic constants and internal

relaxation for monolayer graphene$
Rui Wang , Shaofeng Wang, Xiaozhi Wu, Xiao Liang
Institute for Structure and Function and Department of Physics, Chongqing University, Chongqing 400044, People’s Republic of China

a r t i c l e in fo abstract

Article history: The method of homogeneous deformation is combined with first-principles total-energy calculations on
Received 9 February 2010 determining third-order elastic constants and internal relaxation for monolayer graphene. We employ
Received in revised form density functional theory (DFT) within generalized-gradient-approximation (GGA). The elastic
20 April 2010
constants are obtained from a polynomial fitted to the calculations of strain–energy and strain–stress
Accepted 12 May 2010
relations. Our results agree well with recent calculations by DFT calculations, tight-binding atomistic
simulations, and experiments with an atomic force microscope. The internal relaxation displacement
Keywords: has also been determined from ab initio calculations. The details of internal lattice relaxation by first
First-principles calculations principles are basically consistent with the previous molecular dynamics (MD) simulation. But for tiny
Third-order elastic constants
deformation, there is an anomalous region in which the behavior of internal relaxation is backward
Internal relaxation
action. In addition, we have also demonstrated that the symmetry of the relationship between the
Graphene
internal displacement and the infinitesimal stains can be satisfied.
& 2010 Elsevier B.V. All rights reserved.

1. Introduction
Monolayer graphene, which is a true 2D material of sp2 bonded
carbon systems, has been intensely investigated on the horizon of
materials science and condensed-matter physics. Recently,
graphene has been confirmed as the strongest material ever to
be measured being able to reversible elastic deformations in
excess of 20% [1]. The elastic response of the graphene must be
considered nonlinear because the stress–strain response must
curve over to a maximum point that defines the intrinsic breaking
stress [1]. Moreover, numerical simulations for graphene sheets
have also demonstrated that the nonlinear elasticity should
be considered [2–6]. Besides, for noncentrosymmetric lattice,
internal relaxation is very important to determine the elastic
properties [7] and electron band-structure [8].
In nonlinear elasticity theory, the second-order elastic
constants (SOECs) describe the linear elastic stress–strain
response, including the propagation velocity of acoustic distur-
bances along different crystallographic directions. Higher-order
elastic constants, such as third-order elastic constants (TOECs),
reflect the nonlinear elasticity of the material, including changes
in acoustic velocities due to finite-strain [9,10]. Therefore, both
TOECs and SOECs are very important parameters for modeling the
mechanical repones of lattice under high pressure. In previous
$
The work is supported by the National Natural Science Foundation of China
(10774196).
 Corresponding author. Tel.: + 86 13527528737.
E-mail address: rcwang@cqu.edu.cn (R. Wang).
studies, the TOECs for a wide variety of materials have been
determined from experiments [11]. First-principles calculation
has demonstrated its success in theoretical studies of elastic
properties on various materials.
More recently, several studies have studied the nonlinear
in-plane elastic response and internal relaxation for monolayer
graphene. Liu et al. [2] employed ab initio calculations of
ideal strength and phonon instability by considering nonlinear
elastic response. Cadelano et al. [4] combined continuum
elasticity theory and tight-binding atomistic simulations to
calculate the corresponding moduli, and the density-functional
theory has also used to calculate the nonlinear in-plane
elastic properties by Wei et al. [3]. Zhou et al. [7] developed a
MD approach to directly determine the internal displacement
as a function of the macroscopic strain. In this paper, we
perform first principles calculations of the linear and nonlinear
elastic constants, and obtain the relationships between
the internal relaxation and the applied strain. The internal
relaxation displacement is consistent with the previous MD
simulation [7] in general. But for tiny deformation, it is found
that the behavior of internal relaxation is quite different and
abnormal.
The paper is organized as follows. In Section 2, we recall some
basic facts from nonlinear theory of elasticity, and give the
independent elastic constants. Section 3 contains description of
employed computational methodology. The linear and nonlinear
elastic moduli from first principles calculations are also presented
here. Section 4 deals with the determining of relationship
between internal relaxation and the applied strain.

0921-4526/$ - see front matter & 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2010.05.032
 ARTICLE IN PRESS
3502 R. Wang et al. / Physica B 405 (2010) 3501–3506

2. Nonlinear elasticity theory applied to 2D graphene relationships between the remaining non-zero components and
the independent ones are directly obtained from Eq. (7), as
Our method for calculating elastic constants mentions 0 1
C11 C12 0
finite-strain continuum elasticity theory. Hence, we will recall B C
BC C11 0 C
some basic facts from nonlinear theory of elasticity [12–14], fCij g ¼ B 12 C, ð11Þ
@ 1 A
and apply it on 2D graphene. Let us consider point x¼(x1,x2) 0 0 ðC11 C12 Þ
2
which, after applying strain to a crystal in basal plane, moves
0
to the position x . After introducing the deformation Jacobian and there are two independent elastic constants, C11 and C12,
matrix J, which corresponds to in-plane isotropic linear elasticity for which
@x0i Young’s modulus is E ¼(C211 C212)/C11 and Poisson’s ratio
Jij ¼ , ð1Þ n ¼ C12 =C11 [7]. Also, from Eq. (8) we can directly obtain the
@xj
non-zero third-order elastic constants,
we may define the Lagrangian strain g [14],
C112 ¼ C121 ¼ C211 ,
1X
Zij ¼ ðJ J d Þ, ð2Þ
2 p pi pj ij C133 ¼ C313 ¼ C331 ¼ 13ðC111 þ C112 2C222 Þ,

which is a convenient measure of deformation for an elastic body. C233 ¼ C333 ¼ C332 ¼ 13ð2C111 C112 C222 Þ,
Elastic constants are defined by expanding the internal energy
E as a Taylor series in Lagrangian strain g, C122 ¼ C212 ¼ C221 ¼ 13ðC111 þ 4C112 2C222 Þ, ð12Þ
S0 X S0 X
EðS0 ,fZij gÞ ¼ EðS0 ,0Þ þ C Z Z þ C Z Z Z þ , and there are three independent elastic constants, C111, C112 and
2! ijkl ijkl ij kl 3! ijklmn ijklmn ij kl mn
C222.
ð3Þ Another fundamental quantity in the theory of finite deforma-
tions is Lagrangian stress t
where E(S0,0) and S0 are the corresponding ground state internal
energy and the area of the unstrained graphene, respectively. If 1 @E
tij ¼ , ð13Þ
one uses a notation (xx-1, yy-2, xy-3), which is similar as S0 @Zij
Voigt notation in 3D solid, Eq. (3) can be rewritten as
which can be expressed in terms of true stress tensor r using the
S0 X S0 X following formula:
EðS0 ,fZi gÞ ¼ EðS0 ,0Þ þ C ZZ þ C Z Z Z þ , ð4Þ
2! ij ¼ 1,3 ij i j 3! ijk ¼ 1,3 ijk i j k
t ¼ detð J ÞJ1 rðJT Þ1 : ð14Þ
with the strain tensor becoming the following form:
0 1
1
B Z Z 3. Determination of second- and third-elastic constants
1
2 C
3
g¼B@1
C,
A ð5Þ
Z3 Z2
2 3.1. Computational methodology
where the Cij and Cijk denote here second- and third-order elastic
In the work presented here, we carry out first-principles total-
constants, respectively [14]. If we introduce Jij ¼ dij þ eij and
energy calculations based on the density functional theory (DFT)
assume that eij is symmetric (rotation free) linear strain tensor,
level, using the Vienna ab initio simulation package (VASP 4.6)
the definition of Zij (Eq. (2)) yields
[15–17]. The Perdew–Wang [18] (PW91) exchange-correlation
1X functional for the generalized-gradient-approximation (GGA) is
Zij ¼ eij þ e e : ð6Þ
2 k ik kj used. A plane-wave basis set is employed within the framework
of the projector augmented wave (PAW) method [19,20]. Vacuum
Substituting the above result to the expansion in Eq. (4) and
space of 20 Å normal to graphene plane is used to avoid
leaving only terms up to second order with respect to components
interactions between two layers. Reciprocal space was represent
of eij recover the infinitesimal theory of elasticity.
by Monkhorst-Pack special k-point scheme [21] with 15  15  1
Since the graphene is the 2D hexagonal lattice belonging to
grid meshes. The structures are relaxed without any symmetry
point group D6h, one applies the symmetric transformation T and
constraints with a cut-off energy of 600 eV. To avoid any
has
X wrap-around errors a sufficiently large Fourier grid is used,
Cijkl ¼ Tig Tjh Cghmn Tkm Tln , ð7Þ including all wave-vectors up to twice the cut-off wavenumber.
ghmn The equilibrium theoretical crystal structures for graphene are
X determined by minimizing the Hellmann–Feynman force on the
Cijklpq ¼ Tig Tjh Tkm Cghmnrs Tln Tpr Tqs : ð8Þ atoms and the stress on the unit cell. The convergence of energy
ghmnrs
and force are set to 1.0  10  6 eV and 1.0  10  3 eV/Å, respec-
The elastic constants are the expansion coefficients in the Taylor tively. The geometry optimization for the C–C bond length is
series of Eq. (4) [14], i.e., accurate to 0.001 Å which is very reasonable to reach numerical
 accuracy of the strain–energy and strain–stress, and our calcu-
1 @2 E  lated result 1.424 Å is in good agreement with the experimental
Cij ¼  ðSOECÞ, ð9Þ
S0 @Zi @Zj  value 1.419 Å. To obtain the unit cell for the strained crystal, the
Z¼0
 deformation Jacobian matrix J is applied to the undeformed
1 @3 E  graphene primitive vectors ai to obtain the deformed lattice
Cijk ¼  ðTOECÞ ð10Þ 0
vectors ai,
S0 @Zi @Zj @Zk 
Z¼0 ! ! !
a01 a1 a1
so Cij and Cijk are the symmetric tensor for continuous function ¼ J ¼ ð1þ eÞ, ð15Þ
a02 a2 a2
EðS0 ,fZi gÞ. The independent second-order elastic constants and the
 ARTICLE IN PRESS
R. Wang et al. / Physica B 405 (2010) 3501–3506 3503

and the undeformed primitive vectors for graphene are defined as 0

! 0 a 1 C112
a1 p0ffiffiffi
¼@1 3 A, ð16Þ −500
a2 a a
2 2

Elastic constants (Nm−1)

−1000
where a is the lattice for graphene. The deformation Jacobian
matrix J are determined from the Lagrangian strain g by inverting
Eq. (2). For a given g, the associated deformation Jacobian matrix J −1500
are not unique, the various possible solutions differing from one
another by a rigid rotation. The lack of a one-to-one relationship
−2000
between g and J is not a concern because the calculated energy is
invariant under rigid deformation [22]. For a given applied
deformation, relaxation of the crystal internal coordinates for −2500

the deformed unit cell was performed to obtain the minimized C222
energy for the strained lattice. −3000 C111
The calculated procedure is as follows. To obtain a solvable
system for the TOECs, the number of applied strain tensors must 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
be as large as the number of independent TOECs of graphene. |η |
max
Hence, we consider three sets of deformations parametrized by Z:
Fig. 1. Third-order elastic constants of graphene as a function of the maximum
gA ¼ ðZ,0,0Þ, stain jZmax j including in polynomial fit.

gB ¼ ð0, Z,0Þ,
Table 1
gC ¼ ðZ, Z,0Þ: ð17Þ Comparison of the calculated second- and third-order elastic constants for
monolayer graphene with previous calculations.
The corresponding strain–energy and strain–stress on deforma-
Present results Present results Previous calculations
tion parameter Z for considered types of deformation gA , gB and Strain–energy Strain–stress
gC are expressed as
Energy C11 342 343 347.25a, 353b, 358.1c
C12 64 65 54.99a, 58.2b, 60.4c
DEðgA Þ 1 1 C111  2832  2834  2817c,  2725d
¼ C11 Z2 þ C111 Z3 , C112  390  392
S0 2 6  337.1c, 591d
C222  2684  2686  2693.3c,  2523d

DEðgB Þ 1 1 All data are in units of N m  1.

¼ C11 Z2 þ ðC111 þC133 C233 ÞZ3 ,
S0 2 6 a
Ref. [7], MD simulation.
b
Ref. [23], from bulk graphite.
c
DEðgC Þ 4 Ref. [3], ab initio calculations.
¼ ðC11 þ C12 ÞZ2 þ ðC111 C133 2C233 ÞZ3 : ð18Þ d
Ref. [4], Tight-binding atomistic simulation.
S0 3

Stress

t1 ðgA Þ ¼ C11 Z þ 12C111 Z2 , 3.2. Results and discussion

The calculated results are listed in Table 1, which also provides

t2 ðgB Þ ¼ C11 Z þ 12ðC111 þC133 C233 ÞZ2 ,
t1 ðgC Þ ¼ ðC11 þC12 ÞZ þ ðC111 23 C133 43C233 ÞZ2 ,
t2 ðgC Þ ¼ ðC11 þC12 ÞZ þ ðC111 13 C133 53C233 ÞZ2 ,
where DEðgÞ ¼ EðS0 , gÞEðS0 ,0Þ. An important parameter in these
calculations is the value of maximum strain parameter Zmax
included in the polynomial fit. In this work, the fitted coefficients
for the second-order terms are very stable and are almost
independent of the range of fitting. However, the coefficients for
the third-order term are more sensitive to Zmax . To display this
feature, several TOECs are plotted in Fig. 1 as a function of the
jZmax j in the fitting. The figure shows that the results from the
polynomial fit converge for maximum strain parameters Zmax
above a magnitude 0.04. In every case for gi (i¼ A,B,C), Z is varied
between 0.08 and 0.08 with step 0.005 to obtain accurate
TOECs. For every deformed configuration, the positions of atoms
optimized and both energy and stress tensors are calculated on
the basis of quantum DFT formalism. In this way, for each type of
distortion, dependencies of energy EðgÞ and stress tðgÞ on strain
parameter g are obtained.
our prediction for second- and third-order elastic constants and
compares them with previous calculations [3,4,7,23]. C11 value is
obtained slightly different results from different fits (e.g.,
C11 ¼344 and 340 N m  1 from coefficients in DEðgA Þ=S0 and
DEðgB Þ=S0 , respectively). In such cases, the average of all
obtained values is given in Table 1. The VASP package calculates
the strain–stress relation in 3D materials, so the elastic constants
obtained from strain–stress relation for 2D graphene must be
multiplied by the interlayer spacing 20 Å. The strain–energy
including the results of first principles calculations and the fitted
curves obtained from nonlinear and linear elasticity theory are
shown in Fig. 2. The strain–energies with negative strains are
always larger than ones with positive strains (e.g., see Fig. 2(a),
(b), and (c) for Lagrangian strains gA , gB , and gC , respectively), so
the values of third-order elastic constants Cijk is typically negative.
The presence of the TOECs in strain–energy lead to a lessening of
stiffness at high tensile strains and an increasingly stiff response
at high compressive strains.
Next interesting issue is to examine for which range of strains
the third-order effects really matter. In Fig. 2, we also compare
energy for the deformations with energy values obtained within
linear and nonlinear elasticity theories. One can clearly see that
 ARTICLE IN PRESS
3504 R. Wang et al. / Physica B 405 (2010) 3501–3506

1.4 1.4
First principles results First principles results
nonlinear elasticity nonlinear elasticity
1.2 linear elasticity 1.2 linear elasticity

1 1
Δ E(ηA )/S (Jm−2)

Δ E(ηB )/S (Jm−2 )

0.8 0.8

0.6 0.6

0.4 0.4

0.2 0.2

0 0
−0.08 −0.06 −0.04 −0.02 0 0.02 0.04 0.06 0.08 −0.08 −0.06 −0.04 −0.02 0 0.02 0.04 0.06 0.08
Lagrangian Strain η Lagrangian Strain η

3.5
Finst principles results
nonlinear elasticity
3 linear elasticity

2.5
Δ E(η C )/S (Jm−2 )

1.5

0.5

0
−0.08 −0.06 −0.04 −0.02 0 0.02 0.04 0.06 0.08
Lagrangian Strain η

Fig. 2. Strain–energy relations for 2D graphene. Star points denote results of first principles calculations; solid and dashed lines indicate the curves obtained from
nonlinear and linear elasticity theory, respectively. (a), (b), and (c) describe Lagrangian strains gA , gB , and gC , respectively.

Table 2 with experiment result 340750 N m  1 reported by Lee et al. [1].

Comparison of the calculated linear elastic moduli for monolayer graphene with In Table 2, we list the values of calculated elastic moduli of
the experimental values and previous calculations. Young’s moduli E is in units of monolayer graphene, accompanied by available experimental
N m  1 and Poisson’s ratio n is dimensionless.
data [1] and previous theoretical values [2–4,7,23–26]. In
E n comparison with the previous first principles calculations [3],
we employ GGA-PW91 exchange-correlation functional which
This work 330.4 0.188 seems to be reasonable as well as the GGA-PBE functional for
Ref. [1] 340 7 50 – graphene. The optimized C–C bond length is 1.424 Å, which is
Ref. [2] 350 0.186
more close to the experimental value 1.419 Å than previous result
Ref. [3] 348 0.169
Ref. [4] 312 0.31 1.412 Å obtained from GGA-PBE functional [3].
Ref. [7] 338.5 0.158
Ref. [23] 343 0.165
Ref. [24] 384 0.227
Ref. [25] 345 0.149
4. Internal relaxation displacements
Ref. [26] – 0.173
In continuum elasticity theory, a macroscopically homoge-
neous deformation is described by a constant deformation
Jacobian matrix J (Eq. (1)). Graphene is typically 2D compound
the linear approach is not sufficient for strains larger than lattice and its unit cell contains two atoms which are denoted by
approximately 3.0%. Besides, from Table 1, we obtain Young’s A and B, respectively. Though the deformation for each sublattice
modulus and Poisson’s ratio for the monolayer graphene as can fully described by the macroscopic strain, the displacements
330.4 N m  1 and 0.188, respectively. Young’s modulus agrees well of some atoms in the unit cell do not necessarily follow the same
 ARTICLE IN PRESS
R. Wang et al. / Physica B 405 (2010) 3501–3506 3505

rule for compound lattice. When graphene undergoes a homo- of the vertical bond, denoted by s, as illustrated in Fig. 3(b).
geneous deformation to arrive the equilibrium-deformation state, Recently, Zhou and Huang [7] developed a MD approach to
the atom B does have an internal relaxation [7]. For example, directly determine the internal displacement as a function of the
applying a uniaxial strain ðe11 a0, e22 ¼ 0 and e12 ¼ 0Þ to the unit macroscopic strain. Here, the internal displacement is determined
cell and this procedure is consistent with applying Lagrangian by first principles calculations in which the B atom allow to relax
stain gA , as shown in Fig. 3(a), would stretch the tilted bonds and arbitrarily in-plane to get energy minimization.
change the bond angles, while the length of the vertical bond We show the first principles results of internal displacements
would remain unchanged by assuming homogeneous through applying four types of deformation in Fig. 4. The internal
deformation within the unit cell. The changes of bond angle and displacement s is determined by comparing the position to its
bond length would alter the overlap integral for s electrons, so initial position upon homogeneous deformation. Fig. 4(a)
the internal equilibrium must be maintained by allowing vertical represents the case of the equibiaxial deformation with the
displacements of the atoms that lead to stretching or compressing mean strain, i.e., e11 ¼ e, e22 ¼ e and e12 ¼ 0, and the calculated

Fig. 3. Applying uniaxial strain ðe11 a 0, e22 ¼ 0 and e12 ¼ 0Þ to graphene: (a) without internal relaxation, the atoms are only displaced in the horizontal direction; (b) with
internal relaxation, the two atoms in the unit cell have a relative vertical displacement denoted by s in addition to the horizontal displacement. Meanwhile, the
deformation is still considered homogeneous at the macroscopic sale and the overall shape of the deformed unit cell is same for (a) and (b).

−4
x 10
2 0.025
Internal relaxation displacements (A)

Internal relaxation displacements (A)

τx
0.02 τy

0 0.015

0.01

−2 0.005

−4 −0.005
−0.1 −0.05 0 0.05 0.1 −0.1 −0.05 0 0.05 0.1
Strain ε Strain ε

0.005 0.04
Internal relaxation displacements (A)

Internal relaxation displacements (A)

0
0.02
−0.005

−0.01
0
−0.015

−0.02
−0.02
−0.025

−0.03 −0.04
−0.1 −0.05 0 0.05 0.1 −0.1 −0.05 0 0.05 0.1
Strain ε Strain ε

Fig. 4. The internal relaxation for graphene under applying four sets of strain: (a) denotes the equibiaxial strain (i.e., e11 ¼ e, e22 ¼ e and e12 ¼ 0) without internal relaxation
of atom B within the unit cell. (b) and (c) represent uniaxial strain in the x direction and (i.e., e11 ¼ e, e22 ¼ 0 and e12 ¼ 0Þ and the y-direction (i.e., e11 ¼ 0, e22 ¼ e and e12 ¼ 0Þ,
respectively, and there is only internal relaxation along the y-direction in both the cases. (d) denotes shear mode (i.e., e11 ¼ 0, e22 ¼ 0 and e12 ¼ eÞ, the internal relaxation is
dominated in the x-direction in this case.
 ARTICLE IN PRESS
3506 R. Wang et al. / Physica B 405 (2010) 3501–3506
results e show that internal displacements are less than 10  4 Å, so
these can be negligible. In this case, B atom is always located at
the center of the unit cell and the strained lattice maintains
internal equilibrium without any internal relaxation.
In Fig. 4(b) and (c), we apply the uniaxial deformation along
the x-direction (i.e., e11 ¼ e, e22 ¼ 0 and e12 ¼ 0) and the y-
direction (i.e., e11 ¼ 0, e22 ¼ e and e12 ¼ 0), respectively. Both the
cases, the symmetry maintains the atom B always locating at
midpoint and has no internal relaxation along the x-direction in
unit cell. The relationship between the internal displacements ty
and the strain parameter e is nonlinear and asymmetric for
positive and negative strain e. In small deformations (in the range
0:01 o e o 0:01Þ, it is interesting to find that the linear
approximation for relationship between the internal displace-
ments along the y-direction and the strain is appropriate for both
applying uniaxial strain along the x-direction and the y-direction.
For the strain regions 0:08 o e12 o 0:01 and 0:01 o e12 o0:05
the relationships between internal displacement and strain
parameter e are consistent with the results obtained by Zhou
and Huang using the MD simulation [7], but for the tiny strain
regions 0:01 o e o 0:01, we obtain an opposite trends comparing
with ones obtained by Zhou and Huang [7].
For the shear mode (i.e., e11 ¼ 0, e22 ¼ 0 and e12 ¼ e), we find that
the internal relaxation is dominated and nonlinear in the x-direction,
while the magnitude of relaxation in the y-direction is less than 0.01 Å
for 0:08 o e12 o0:08 in Fig. 4(d). The relationship between the
internal relaxation displacement and the shear strain e12 is symmetric
with respect to the positive and negative shear strains. For the strain
regions both 0:08 o e12 o 0:01 and 0:01 o e12 o0:08, tx has linear
relationships with same scale coefficient  0.5035 Å, which is good
agreement with the value 0.5779 Å obtained by MD simulation [7].
For tiny shear strains (in the range 0:01 o e12 o0:01Þ, the linear
relationship is also appropriate but has scale coefficient 0.1621 Å,
which has not been obtained by MD simulation [7].
Through the above discussions, we find that the internal relaxation
from our first principles calculations is basically consistent with the
previous results obtained from the MD simulation [7] for strain
regions 0:08 o e o0:01 and 0:01 o e o 0:05, but it is backward for
tiny strain 0:01o e o 0:01. The DFT results for the total energy
combined with the strain-relaxation relation have enabled us to
determine internal displacement s. The comparison to the previous
MD study (Ref. [7]) seems to shed some light on the puzzling
discrepancy on the predicted Young’s modulus of graphene by the
first-principle and MD calculations. As discussed in Ref. [7], Young’s
modulus predicted by MD would have compared closely to the first-
principles calculations if the internal relaxation is turned off.
However, with internal relaxation, the MD-predicted Young’s
modulus is considerably lower. The present study (Fig. 4, in particular)
seems to suggest that the internal relaxation is indeed negligible
under infinitesimal strains (o0:01) based on the first-principles
calculations.
Since the linear relationships are appropriate for tiny strain,
we can write internal relaxation displacement s as
X Landolt-Böstein, New Series, Group III, vol. 29A, Springer, Berlin, 1992.
ti ¼ Dijk ejk : ð19Þ
jk
Because stain tensor eij is symmetric tensor, the coefficients
satisfy
Dijk ¼ Dikj , ð20Þ
and their values can be obtained by fitting the DFT results, as
D111 ¼ D122 ¼ D212 ¼ 0,D211 C D222 C 0:10 Å, and D112 C0:08 Å.
The symmetry of the 2D hexagonal lattice requires
X [24] K.H. Michel, B. Verberck, Phys. Status Solidi B 245 (2008) 2177.
Dijk ¼ Tim Tjn Tkl Dmnl , ð21Þ
mnl
with symmetric operator T. We p can
ffiffiffi directly obtain
D111 ¼ D122 ¼D212 ¼0 and D211 ¼ D222 ¼ 3D112 from Eq. (21).
We must point out that the values of D122 and D222 is always
equivalent but with opposite sign in any strain range, because of
the equibiaxial deformation without any internal relaxation. The
coefficients Dijk obtained from the symmetry are in good
agreement with the first principles results.
5. Conclusions
We present first principles calculations on the nonlinear elastic
properties and internal relaxation for monolayer graphene. In our
method, second- and third-order elastic constants for graphene
are determined from applying three sets of homogeneous elastic
deformation. We have used two approaches involving either
strain–energy or strain–stress relations, obtaining consistent
results from both of them. The values of the third-order elastic
constants are in good agreement with the previous calculated
results, and the linear elastic moduli is also consistent with
previous experimental and theoretic values. The linear approach
is not sufficient for strains larger than approximately 3.0%.
Through applying homogeneous in-plane strain, we have also
determined the internal relaxation displacement. The results
shows that nonlinear relationship between the internal relaxation
displacement and the applied strain, which is basically consistent
with the previous MD simulation [7]. In tiny deformation
(approximately 0:01 o e o 0:01Þ, the relationship between the
internal relaxation displacement and the applied strain is back-
ward from the result obtained from MD simulation [7]. The
unified expression of linear relationships between the internal
relaxation displacement and the applied strain in the tiny
deformation has been obtained. In addition, we have also
demonstrated that the symmetry for the relationship between
the internal displacement and the tiny strain can be satisfied. Our
study seems to suggest that the internal relaxation is indeed
negligible under infinitesimal strains ð o 0:01Þ based on the first-
principles calculations.
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