Physica E 115 (2020) 113701

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Physica E: Low-dimensional Systems and Nanostructures

journal homepage: http://www.elsevier.com/locate/physe

Hydrogenated ψ-graphene: Band gap engineering and optical properties

Xiaoming Huang a, Mengyao Ma a, Li Cheng b, Lizhao Liu b, c, *
a
School of Ocean Science and Technology, Dalian University of Technology, Panjin Campus, Panjin, 124221, China
b
School of Mathematical and Physical Sciences, Dalian University of Technology, Panjin Campus, Panjin, 124221, China
c
Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Dalian University of Technology), Ministry of Education, Dalian, 116024, China

A R T I C L E I N F O A B S T R A C T

Keywords: Hydrogen passivation was predicted to be an effective method to open the band gap of ψ-graphene by the density
ψ-graphene functional theory calculations. A critical H coverage of ~60% was found, above which the hydrogenated
Hydrogen passivation ψ-graphene opens a band gap. The band gap can be tailored within a wide range of 0–3.57 eV by changing the H
Band gap engineering
coverage. Meanwhile, the opened band gap brings the hydrogenated ψ-graphene different optical properties from
Optical property
the pristine ψ-graphene. Generally, the ψ-graphene possesses the major absorption peaks similar to graphene,
except for the redshift of sub-π peak features caused by the pentagons and heptagons. However, hydrogen
passivation can result in quite different optical properties from the pristine ψ-graphene for both the absorption
peaks and delay. As the H coverage decreases, the absorption coefficient of the hydrogenated ψ-graphene drops
independently on the light polarization. Particularly, the absorption delay will be improved during removing the
H atoms due to lowering of band gap, which is useful for selective optical absorption.

1. Introduction
In the fabrication and application fields of graphene, pentagons and
heptagons are usually regarded as defects, which may play prominent
roles on the properties of graphene [1–4]. However, recent predictions
show that pentagons and/or heptagons can even serve as building blocks
for novel two-dimensional (2D) carbon nanomaterials, such as
penta-graphene [5], phagraphene [50] or ψ-graphene [6], and
Stone-Wales graphene [7], just like the cases (e.g. carbon nanotorus and
carbon nanocoil) in carbon nanotubes [8]. The penta-graphene
completely composes of pentagons with coexistence of sp2 and sp3 car­
bon atoms, exhibiting a large indirect band gap above 2.2 eV [5,9,10]
and a negative Poisson’s ratio of 0.068 [5]. On the other hand, the
ψ-graphene and Stone-Wales graphene are formed of pentagons, hexa­
gons and heptagons with only sp2 carbons. Quite different from the
penta-graphene, the ψ-graphene is metallic due to no sp3 carbons.
The metallicity of ψ-graphene limits its applications in electronics
and optoelectronics. Therefore, band-gap engineering is essential to
ψ-graphene. As for band-gap engineering of graphene, there are several
possible methods, such as strain [11–13], doping [14–18], introducing
vacancies, and surface adsorption [19,20] or passivation [21–23]. Both
the uniaxial and shear strains can open the band gap of graphene
through shifting the Dirac cones, but only result in a small band gap
within 0.72 eV [13]. Band gap engineering by doping is closely related
to the dopants and doping density. Some dopants can increase the band
gap but some will lead to a gap decrease instead [14]. The surface
passivation is an effective way to tailor the band gap of graphene
through introducing sp3 carbons. It was suggested that hydrogen
passivation can continuously open the band gap of graphene up to
4.66 eV at the fully H-passivated configuration, i.e. graphane [23].
The opened band gap of graphane also brings the different optical
properties from its graphene precursor. For in-plane polarization (E ? c),
the absorption spectrum indicates an optical metallicity of graphene
with a singularity at zero frequency [24,25], but shows a semi­
conducting property of graphane [26–28]. Moreover, the absorption
peaks of graphane shift a lot away from these of graphene for both the
in-plane and out-of-plane (E k c) light polarization. The main absorption
peaks of graphane locate at 9.8 and 11.7 eV for E ? c, and 6.8 and
13.2 eV for E k c [27], away from those of graphene (4 and 14 eV for E ?
c, and 11 and 14 eV for E k c) [24]. Besides, transition from valence band
maximum to conduction minimum is forbidden for the graphane since
the absorption is zero in the band gap region [27]. Thus, band gap en­
gineering is also important for the optical applications of
graphene-based materials.
Inspired by the band-gap engineering of graphene by hydrogen
passivation, employing the density functional theory (DFT) we

* Corresponding author. School of Mathematical and Physical Sciences, Dalian University of Technology, Panjin Campus, Panjin, 124221, China.
E-mail address: lizhao_liu@dlut.edu.cn (L. Liu).

https://doi.org/10.1016/j.physe.2019.113701
Received 3 July 2019; Received in revised form 27 August 2019; Accepted 2 September 2019
Available online 3 September 2019
1386-9477/© 2019 Elsevier B.V. All rights reserved.
X. Huang et al. Physica E: Low-dimensional Systems and Nanostructures 115 (2020) 113701

Fig. 1. Schematic to show the process of exploring the stable model of ψ-graphane from adding one (a) and two (b) H atoms to twelve H atoms (c). The inequivalent
carbon atoms are highlighted in grey different color depths, and the hydrogen atoms are highlighted in light blue. (For interpretation of the references to color in this
figure legend, the reader is referred to the Web version of this article.)

investigated the hydrogenated ψ-graphene, aiming to tailor the elec­
tronic and optical properties of ψ-graphene by hydrogen passivation. It
was found that hydrogen passivation is an effective approach to open the
band gap of ψ-graphene in a wide range and brings different optical
properties, which should be useful for the application of ψ-graphene in
nanodevices.
2. Computational methods
Vienna ab initio simulation package (VASP) [29] based on the
plane-wave pseudopotential technique was employed for the DFT cal­
culations. The exchange-correlation interaction was described by the
Perdew-Burke-Ernzerhof (PBE) functional within the general gradient
approximation (GGA) [30] and the ion-electron interaction was treated
with the PAW pseudopotential [31,32]. The Monkhorst-Pack k-mesh
grid [33] of 0.01 Å 1 and a well-tested value of 520 eV for kinetic energy
cutoff were used to ensure the convergence of total energy. To avoid the
interaction between the structure and its periodic images, a vacuum
thickness of ~18 Å was adopted. All the structural models were fully
relaxed using the conjugate gradient algorithm until the force on each
atom was less than 0.01 eV Å 1 and the energy was converged to
10 6 eV. Based on the equilibrium structures, both the electronic and
mechanical properties of hydrogenated ψ-graphene were calculated by
using the same scheme.
The optical properties were calculated using the linear response
method within the random phase approximation (RPA) approach with
including changes of the Hartree and the exchange correlation potential
[34]. The dielectric function ε(ω) can be written as:
εðωÞ ¼ ε1 ðωÞ þ iε2 ðωÞ:
The real part ε1 ðωÞ in form of the 3 � 3 Cartesian tensor εαβ was
ð1Þ
calculated by:
Z ∞ εð2Þ ’ ’ atoms prefer to locate at two neighbor carbon atoms up and down,
2 αβ ðω Þω
εð1Þ
αβ ðωÞ ¼ 1 þ P dω’ ;
π ω ’2 ω2
0
k. Then, the adsorption coefficient a(ω) can be further obtained from the
ε(ω) by the following equation:
�pffiffi � �qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi �1=2
aðωÞ ¼ 2 ω ε1 ðωÞ2 þ ε2 ðωÞ2 ε1 ðωÞ : (4)
So far, the DFT method has been greatly improved and proven to be
one of the most accurate methods to calculated the properties of most
solids, including the electronic [35–37], thermoelectric [38–40], and
optical [41–45] properties. Thus, the theoretical results presented here
are reliable and useful to the real applications of ψ-graphene.
3. Results and discussion
3.1. Structural models
Based on idea of hydrogenated graphene [23], we first explored the
stable model of fully hydrogenated ψ-graphene through comparing the
binding energy (Eb), which is defined as:
��
Eb ¼ Ehydrogenated ψ graphene Eψ graphene nEH n; (5)
where Ehydrogenated ψ -graphene, Eψ -graphene and EH are the total energies of
hydrogenated ψ-graphene, ψ-graphene and an isolated H atom respec­
tively. The n is the number of H atoms in the hydrogenated ψ-graphene.
Similar to the definition of graphane, the fully hydrogenated ψ-graphene
is called ψ-graphane hereafter.
According to Li et al.’s report [6], there are four inequivalent carbon
atoms in the unit cell of ψ-graphene, as labeled by C1, C2, C3 and C4 in
Fig. 1. To find the optimal sites for adding H atoms, we first placed one H
(1) atom in the four inequivalent sites separately. It was found that C1, the
one shared by a pentagon and a heptagon, is the best site for adding one
H atom with a binding energy of 2.68 eV/atom, as illustrated in
Fig. 1a. Afterwards, we put two H atoms in different sites. The two H
(2) agreeing well with the case of graphane [21,46]. As a result, there are
five possible structures for adding two H atoms, with the two H atoms in

where P is the principal value. On the other hand, The imaginary part (C1, C1), (C1, C2), (C2, C3), (C2, C4) and (C3, C4) respectively. Through
comparing the binding energy, the structure with H atoms siting in (C2,
ε2 ðωÞ in form of the 3 � 3 Cartesian tensor εð2Þ
αβ was obtained from the
C3) is the most stable one with a binding energy of 3.09 eV/atom
equation of states [34]:
among the five structures, as shown in Fig. 1b. According to the rule of
4π 2 e2 1 X up-and-down H pairs, we finally obtain the stable structure of
εð2Þ
αβ ðωÞ ¼ lim 2w!δðεc! εv! ωÞ � ⟨uc! ! ju !⟩
k þe q v k ψ-graphane will fully covered H atoms with a binding energy of
Ω q→0 q2 ! k k k α

c;v; k (3) 3.59 eV/atom, as shown in Fig. 1c. It can be noticed that due to the
� ⟨u ! ! juv! ⟩* ; existence of pentagons and heptagons in ψ-graphane, some H atoms
c k þ e βq k
must lie in the same side, but still form the up-and-down patterns be­
where Ω is the volume of the primitive cell, q is the magnitude of the tween two neighbor sameside H pairs, as marked by a red oval in Fig. 1c.
Bloch vector of the incident wave ! q , c and v correspond to the con­ To investigate the effect of H coverage, we started from a 4 � 4
! ψ-graphane supercell of 100% H coverage, which has 192 C atoms and
duction and valence band states, k is the Bloch wave vector, ! e α and !
eβ 192 H atoms, i.e. C192H192. Then, the hydrogenated ψ-graphene with
are the unit vectors for the three Cartesian directions, w! is the k-point different H coverages can be obtained by removing the H atoms. As
k
weight, and u is the cell periodic part of the wavefunction at the k-point mentioned above, there are two kinds of H pairs, lying up and down and

2
X. Huang et al.
Fig. 2. Schematic to remove the sameside H pairs row by row. Each row of
sameside H pairs were masked in shadow. By removing one to four rows of
sameside H pairs, the hydrogenated ψ-graphene models with the chemical
formulae C192H176, C192H160, C192H144, and C192H128 were obtained.
in the same side. It was found that the energy cost of removing one
sameside H pairs was 0.04 eV/atom lower than removing one up-and-
down H pairs. Moreover, removing two neighbor sameside H pairs
like the case highlighted by red oval in Fig. 1c is easier than removing
one sameside H pairs. Therefore, we first removed the sameside H pairs
row by row. In the 4 � 4 ψ-graphane supercell, there are four rows of
sameside H pairs. By removing them row by row, the structural models
with H coverages of 91.7% (C192H176), 83.3% (C192H160), 75%
(C192H144), and 66.7% (C192H128) can be obtained respectively, as pre­
sented in Fig. 2. Further decreasing the H coverage will remove the up-
and-down H pairs. In this case, following the work on hydrogenated
graphene [23], the Monte Carlo method was adopted to randomly
removed the up-and-down H pairs. For each H coverage, we randomly
Fig. 3. DOS of the hydrogenated ψ-graphene with different H coverages (a–c) and band gap dependence on the H coverage (d). The Fermi energy is set to be zero.
3
Physica E: Low-dimensional Systems and Nanostructures 115 (2020) 113701
generated 10 structures. After optimization, two optimal structures with
low energy were kept for further study of electronic properties.
3.2. Electronic properties
To demonstrate the role of H coverage on tailoring the band gap of
ψ-graphene, the electron density of states (DOS) of hydrogenated
ψ-graphene models with different H coverages were calculated. As
shown in Fig. 3a, the ψ-graphane at 100% H coverage is an insulator
with a large band gap of 3.57 eV. No defect states were found near the
Fermi energy. This indicates that hydrogenation is an efficient way to
tune the electronic properties of ψ-graphene, making the metallic
ψ-graphene be insulating. Further removing the H atoms will decrease
the band gap. In particular, the H coverage of 60.4% is a critical point.
For the hydrogenated ψ-graphene at 60.4% H coverage, the most stable
one among the 10 randomly generated structures is metallic, as shown in
Fig. 3b, but the second stable one is semiconducting with a small band
gap of 0.58 eV, as shown in Fig. 3c, which is only 0.005 eV/atom higher
in binding energy than the most stable one. After this critical point, the
hydrogenated ψ-graphene with lower H coverage is always metallic.
We further plotted the relationship between the band gap and the H
coverage to illustrate a clear dependence of band gap on the H coverage,
as presented in Fig. 3d. It can be noticed that once removing one row of
sameside H pairs, the band gap drops sharply from 3.57 eV at 100% H
coverage to 2.31 eV at 91.7% H coverage, with a decrease ratio of 35%.
Continuously removing the sameside H pairs leads to a gentle decrease
of band gap from 2.31 eV at 91.7% H coverage to 2.16 eV at H coverage
of 66.7% with only 7% decrease. However, during further removing the
up-and-down H pairs, the band gap drops dramatically again from
2.16 eV at H coverage of 66.7% to ~1.50 eV at 63.5% H coverage.
X. Huang et al.
Fig. 4. Imaginary part of dielectric function (Imε) of the ψ-graphene and ψ-graphane for E ? c (a) and E k c (b), as well as the DOS of the ψ-graphene (c) and
ψ-graphane (d).
Particularly, the H coverage of 60.4% is a critical point where the hy­
drogenated ψ-graphene begins to be metallic. Below this critical H
coverage, the hydrogenated ψ-graphene structures will be metallic, such
as the one with an H coverage of 55.2%. Previously, it was found that the
hydrogenated phagraphene with 60% H coverage has a band gap
ranging from 2.65 to 0 eV depending on the structural details [51].
Therefore, the critical H coverage predicted here is quite consistent with
that in hydrogenated phagraphene.
In general, H passivation is an effective way to tailor the band gap of
ψ-graphene, which can achieve continuous gap opening up to 3.57 eV.
The tunable band gap of hydrogenated ψ-graphene makes it promising
in electronics and optoelectronics.
3.3. Optical properties
In addition to the band gap engineering, we also considered the ef­
fect of H coverage on the optical properties of hydrogenated ψ-gra­
phene. First, the imaginary part of dielectric function (Imε) was plotted
to study the optical absorption properties of both the ψ-graphene and
ψ-graphane, as well as the graphene for comparison. As shown in Fig. 4a,
for E ? c, the Imε of graphene shows two pronounced peaks at 4 and 14
eV, which originated from π→π* and σ→σ* interband transitions sepa­
rately [24]. The calculated Imε of graphene agrees well with previous
reports [24,25,47], indicating the validity of our method. The Imε of
ψ-graphene generally resembles the feature of graphene with two main
peaks at 2.6 and 14 eV. From the DOS shown in Fig. 4c, the peak at
2.6 eV results from the electron transition of C 2pz orbitals to C 2pz or­
bitals, which is due to π→π* interband transition [24]. Then, the peak at
14 eV is mainly contributed from the electron transition of C 2s, C 2px
and C 2py orbitals to C 2s, C 2px and C 2py orbitals, corresponding to
σ→σ* interband transition since the σ electrons come from sp2 hybrid­
ization [24]. However, compared with the 4 eV peak from π→π* tran­
sition of graphene, the 2.6 eV peak of ψ-graphene shows a prominent
redshift. This redshift can be explained by the topology-induced reso­
nant π states due to existence of pentagons and heptagons in ψ-graphene
[48], as indicted by the increased in the local density of states near the
4
Physica E: Low-dimensional Systems and Nanostructures 115 (2020) 113701
Fermi level [6]. Since the long range pentagon/heptagon defects only
play remarkable roles below the π plasmon energy [49], the 14 eV peak
contributed by σ→σ* transition of graphene is well kept in ψ-graphene.
Moreover, the Imε of ψ-graphene is similar to the cases of B/N-doped
graphene [25], which can be simply understood by considering the
pentagon as B doping and heptagon as N doping. On the other hand, due
to the hydrogen passivation in ψ-graphane, the absorption peaks shift a
lot from those of ψ-graphene in E ? c. As shown in Fig. 4a, the two
absorption peaks of ψ-graphane locate at 10.7 and 12.7 eV, with a
blueshift to those (9.8 and 11.7 eV) of graphane [27]. From the DOS
presented in Fig. 4d and the reported data of graphane [27], we can infer
that the peak at 10.7 eV is due to the electron transition of C 2p and H 1s
orbitals to C 2p orbitals, and the one at 12.7 eV originates from the
electron transition of C 2s, C 2p and H 1s orbitals to C 2p orbitals.
Then, for E k c shown in Fig. 4b, the Imε of graphene has two peaks at
11 and 14.5 eV originated from π→σ* and σ→π* transitions respectively,
also consistent with previous reports [24,25,47]. The prominent ab­
sorption in the frequency of the ψ-graphene ranges from 10 to 18 eV,
with three peaks at 11, 13 and 16 eV. According to the DOS of the
ψ-graphene in Fig. 4c, we can infer that the peak at 11 eV mainly roots
from the electron transition of C 2pz orbitals to C 2s, C 2px and C 2py
orbitals, which is believed to be π→σ* transition [24]. Then, the peaks at
13 and 16 eV come from the electron transition of C 2s, C 2px and C 2py
orbitals to C 2pz orbitals, which is σ→π* transition [24]. Compared with
graphene, the electron localization [6] induced by pentagon-heptagon
defective rings may cause the relative high intensity of 16 eV peak in
ψ-graphene, similar to the cases of local field effects [24]. In addition,
the ψ-graphane has two peaks located at 6.8 and 13.5 eV, which are the
same as the case of graphane [27]. From the DOS of ψ-graphane shown
in Fig. 4d, the peak at 6.8 eV is mainly resulted from the electron tran­
sition from the higher occupied C 2p orbitals to the lower unoccupied C
2p orbitals. Then, the 13.5 eV peak mainly comes from the electron
transition from the lower occupied C 2p and H 1s orbitals to the C 2p
orbitals. However, compared with graphane, the relative intensity of
8.5 eV peak in ψ-graphane is degraded due to incorporation of penta­
gons and heptagons, similar to the effect of Stone-Wales defects [28].
X. Huang et al.
Fig. 5. Absorption coefficient of the hydrogenated ψ-graphene with different H coverages for E ? c (a) and E k c (b).
Particularly, in the band gap area (3.57 eV) of ψ-graphane, the Imε is
zero for both the E ? c and E k c, which implies there is no direct
transition from the valence band maximum to the conduction band
minimum, agreeing well with graphane [27]. Besides, significant ab­
sorption delays can be observed, which are 2.8 eV for E ? c and 1.4 eV
for E k c. Also, the different optical response for E ? c and E k c indicates
the optical anisotropy of ψ-graphane.
Afterwards, absorption coefficient spectra of the hydrogenated
ψ-graphene with different H coverages were presented to show the effect
of H coverage on the optical properties. As shown in Fig. 5a, for E ? c,
the hydrogenated ψ-graphene always possesses the major absorption
peaks at ~11.8 and ~13.0 eV despite of the H coverage. While, the
absorption coefficient of the two peaks degrades smoothly with a
descent ratio of ~9% as the H coverage decreasing from 100% to 60.4%.
However, since decreasing the H coverage will drop the band gap of the
hydrogenated ψ-graphene, the absorption delay is highly improved. For
the H coverage ranging from 91.7% to 66.7%, the absorption starts from
the photon energy of ~2.5 eV, with a delay of only ~0.2 eV. Moreover,
removing H pairs bring the feature of graphene with an absorption peak
at 4.0 eV due to π→π* interband transition. The more H pairs are
removed, the more features of graphene appear.
On the other hand, for E k c illustrated in Fig. 5b, the absorption
coefficient of the major peak at 13.5 eV drops remarkably as the H
coverage decreasing. The descent ratio from 100% to 60.4% H coverage
even reaches ~40%, much higher than the change of major peak for E ?
c. But, the absorption coefficient at the 6.8 eV peak only slightly de­
creases with removing the H atoms. Moreover, as the H coverage
changes, both the 6.8 and 13.5 eV peaks have a slight shift, especially for
the 60.4% H coverage. Also, the photon energy at which the absorption
begins gradually decreases with lowering the H coverage due to nar­
rowing of band gap in the hydrogenated ψ-graphene.
4. Conclusions
Employing the DFT calculations, the hydrogenated ψ-graphene was
modeled, aiming to study the electronic and optical properties. It was
demonstrated that hydrogen functionalization is feasible to tailor the
band gap of ψ-graphene. As the H coverage changes, a critical H
coverage of ~60% was obtained where the hydrogenated ψ-graphene
begins to open a band gap and the band gap reached the maximum of
3.57 eV at the H coverage of 100%. Moreover, hydrogen passivation also
plays an important role on the optical properties of the ψ-graphene.
Without hydrogen passivation, the ψ-graphene generally resembles the
feature of graphene with peaks at 2.6 eV from π→π* interband transition
5
Physica E: Low-dimensional Systems and Nanostructures 115 (2020) 113701
and 14 eV from σ→σ* interband transition for E ? c, and with peaks at
11 eV from π→σ* transition and 14.5 eV from σ→π* transition for E k c.
However, hydrogen passivation can lead to quite different optical
properties. The absorption peaks of the ψ-graphane shift a lot from those
of the pristine ψ-graphene for both the in-plane and out-of-plane po­
larization. As the H coverage decreases, the absorption coefficient of the
hydrogenated ψ-graphene drops for both the E ? c and E k c. Especially,
the absorption delay is remarkable reduced during lowering the H
coverage. Therefore, the tunable electronic and optical properties of
ψ-graphane by controlling the H coverage make it promising in device
applications.
Conflicts of interest
The authors declare no conflict of interest.
Acknowledgements
This work was supported by the National Natural Science Foundation
of China (Nos. 11504040, 11604039 and 11574040), and the Funda­
mental Research Funds for the Central Universities of China (Nos.
DUT16RC(4)66, DUT16LAB01, DUT16LK03 and DUT18LK07). L.Z. Liu
acknowledges the support by the State Key Laboratory of Low-
Dimensional Quantum Physics, Tsinghua University (KF201804). The
calculations are supported by Supercomputing Center of Dalian Uni­
versity of Technology.
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