Struct Chem (2015) 26:731738
DOI 10.1007/s11224-014-0531-2
REVIEW ARTICLE
First-principles study of hydrogen storage on Pt (Pd)-doped boron
nitride sheet
Juan Ren NingChao Zhang Hong Zhang
XiaoJuan Peng
Received: 15 August 2014 / Accepted: 20 October 2014 / Published online: 8 November 2014
Springer Science+Business Media New York 2014
Abstract We report a first-principle study of hydrogen
adsorption on Platinum (Pt)- and Palladium (Pd)-doped
hexagonal boron nitride sheet. The results show that both
isolate Pt and Pd atoms are preferred to locate on the top of
N atom with binding energies of 5.028 and 4.113 eV,
respectively. A maximum of three hydrogen molecules can
chemically bind to single Pt/Pd atom, respectively, with the
HH bonds of H2 molecules significantly elongated. The
average binding energies per H2 molecule for Pt-/Pd-doped
BN sheet are around 1.010 and 0.705 eV, which is higher
than that of the pristine-BN sheet. In addition, more H2
molecules would bind with metal-doped BN sheet when
more metal atoms are dispersed at the BN sheet. Our cal-
culations offer explanation for the nature of bonding
between the metal atom and the hydrogen molecules,
which is mainly due to the Kubas interaction and the
polarization mechanism.
Keywords Hydrogen storage  Density functional
calculations  Pt-/Pd-doped  Boron nitride  Adsorption
J. Ren (&)
School of Science, Xian Technological University,
Xian 710032, China
e-mail: rjrj1107@163.com
J. Ren  H. Zhang
College of Physical Science and Technology, Sichuan
University, Chengdu 610065, China
N. Zhang
College of Electronics and Information Engineering, Xian
Technological University, Xian 710032, China
X. Peng
Institute of fluid physics, China Academy of Engineering
Physics, Mianyang 621900, China
Introduction
Hydrogen is considered as one of the best energy carriers
because of its abundance in nature [13] and combustion
creating neither air pollutants nor greenhouse. However, it
has not been available for commercial use yet, because of
several hurdles that are needed to be overcome [4, 5]. One
of the most difficult challenges in realizing a hydrogen
economy is synthesizing materials that can store hydrogen
with high gravimetric and volumetric density at near-
ambient thermodynamic conditions [6, 7]. In the past few
years, a lot of materials have been tested for hydrogen
storage; however, to date, no technology has been devel-
oped that meets all DOE targets, and problems in size,
durability, cost, safety, and other factors impede the
broader adsorption of onboard H2 storage technologies.
During the past decade, the carbon-based materials have
been considered as promising media for hydrogen storage
[8, 9]. However, due to the very weak physical adsorption
of H2 for most materials including carbon-based materials,
recent efforts have been directed that non-carbon nano-
systems composed of light elements such as B and N offer
many advantages to store hydrogen, such as the possibility
of good reversibility, fast kinetics, and large surface area
[1012]. Furthermore, carbon-based materials are oxidized
at 600 C, while the BN materials are stable up to
1,000 C [13]. Boron nitride can exist in a hexagonal
structure h-BN similar to the graphite sheet structure.
Among the pioneering works in this field, Corso et al. [14]
have been successful to produce h-BN nanomesh on Rh
(1 1 1) single crystalline surface by self-assemble. And
later, Novoselov et al. [15] obtained BN sheets using
mechanical cleavage. These breakthrough experiments
may pave the way for future application of the h-BN sheet
in many fields, such as gas storage, electronic devices, and
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templates for assembling specific nanostructures [1618].
Unfortunately, the binding energy of molecular hydrogen
to boron nitride substrate is very weak, about -0.09 eV/H2
[19, 20]. For practical vehicular hydrogen storage appli-
cations, the molecular binding energy should be of order
-0.2 to -0.7 eV/H2. Many investigations show that simply
van der Waals surfaces are not enough to have good
adsorption energy of gas molecules, and the presence of an
ionic site can improve the property [21]. H2 is trapped
around the dispersed doping atoms through electronic and
polarization interaction. Previous experimental and theo-
retical studies have shown that doping alkali metal or
transition metal (TM) on BN and carbon systems could
appreciably improve hydrogen uptake due to the enhanced
adsorption energy of H2 [2224]. Tang et al. investigations
show that the hydrogen storage capacity can reach to 4.2
wt% if BNNT were doped with Pt atom [25]. The defective
[26], Li-doped [27], Ti-doped [28], and Pt-doped [29] BN
nanostructures show enhanced adsorption ability. Very
recently, Venkataramanan et al. [30] found that hydrogen
binding properties of boronnitride systems are strongly
dependent on the Ni and Rh atoms doped on the sheets.
Those suggest that doping with impurities may allow to
tuning the properties and the chemical sensitivity of BN
nanostructures.
In this work, the H2 molecules adsorption properties
upon Pt-/Pd-doped BN sheet are investigated using first-
principles calculations. We first consider the interactions of
metal atoms (Pt and Pd) on h-BN sheet. Then the hydrogen
adsorption and maximum number of H2 molecules on
single Pt and Pd atoms are investigated so as to understand
the nature of hydrogen interaction with metal functional-
ized BN sheet. Since transition metal atoms tend to cluster
once they meet each other at high doping concentration.
We also study the effect of hydrogen storage upon more
metal atoms doped substrate.
Methods
The calculations were performed using the CASTEP code,
which is based on spin-polarized density functional theory
and plane-wave pseudopotential method [31]. The Perdew
Wang 91 (PW91) form was used for the generalized gra-
dient approximation (GGA) to exchange and correlation
potential [32]. Previous benchmark calculations showed
that the results using the PW91 functional are close to those
obtained from the second-order MollerPlesset (MP2)
perturbation level of theory for describing the noncovalent
intermolecular interactions [3335]. The valence states for
all potentials used here are 1s for H, 2s22p1 for B, 2s22p3
for N, 4d10 for Pd, and 5d96s1 for Pt, respectively. The
energy cutoff for the plane-wave basis set was 300 eV. The
123
Struct Chem (2015) 26:731738
convergence for the energy and the force were set to
2 9 10-5 eV and 0.05 eV/A , respectively. The surface
model was modeled using a supercell containing 50 atoms,
with a vacuum region 20 A perpendicular to the sheet plane
in order to eliminate the interaction between periodic
images. We used 5 9 5 9 1 k-point mesh to sample the
2D brillouin zone (BZ) during geometry optimization and
7 9 7 9 1 k-grids are further used to obtain the properties
of all systems.
To investigate the changes of electronic structures in h-
BN sheet caused by the adsorption of metal atom, electron
density difference Dq is calculated, which illustrates how
the charge density changes during this doping process. Dq
is defined as
 
Dq qtotal  qBN qPt=Pd
in which qtotal, qBN, and qPt/Pd, denote electron density of
the Pt-/Pd-doped BN, BN sheet, and Pt/Pd atom,
respectively.
Results and discussion
Before studying hydrogen adsorption on metal (Pt, Pd)
functionalized h-BN sheet, pure and metal functionalized
BN sheet systems are investigated. The relaxed BN bond
length in a bare h-BN sheet is calculated to be 1.449 A , is in
good agreement with experimental value of 1.450 A [36, 37].
To obtain a legitimate comparison, with adatom adsorption
on h-BN sheet, it is important to determine the energetically
favorable adsorption. To do this, as shown in Fig. 1a, we
consider four possible different initial sites to adsorb Pt/Pd
atom, including (1) the on top of the B atom (B); (2) the on-
top of the N atom (N); (3) the center of the hexagon (H); and
(4) the bridge site over BN bond (BN). The metal adsorption
energy of the functionalized BN sheet is defined as Ea =
E(BN) ? E(M)-E(BN?M), where E(BN?M) is the total energy
of fully relaxed Pt-/Pd-doped BN sheet, and E(BN) and E(M)
are the energies of the pure BN sheet and isolated metal
atom, respectively. By definition, a positive value of Ea
corresponding to exothermic adsorption. As shown in
Fig. 1b, after full structural optimization, Pt atom is found to
locate on the top of N, regardless of the initial location of the
Pt atom. It indicates that the Pt atom is more stable on the N
site than other sites. For the case of Pt-doped BN system, the
adsorption energy at the N site is 5.028 eV, and the PtN
bond is calculated to be 2.044 A . The distance of BN around
the Pt atoms is slightly elongated from 1.450 to 1.488 A . The
most stable structure of the Pd atom-doped BN sheet was
found to be N site, while the bridge site is less stable by
4.103 eV. For the Pd atom, the distance of NPd was found
to be 2.124 A with adsorption energy of 4.113 eV, as shown
in Fig. 1c.
Struct Chem (2015) 26:731738
Fig. 1 a The optimized
geometric structure of BN
sheet along with the four
possible sites of metal doping.
The optimized and most stable
structures of b Pt atom doped on
BN sheet and c Pd atom doped
on BN sheet. d Density of states
of pure, Pt-doped, and Pd-doped
BN sheet. The Fermi level is set
to zero
According to the Mulliken charge analysis of single Pt
and Pd atoms adsorbed on BN sheet, Pt and Pd atoms carry
0.25 and 0.17 e, respectively, indicating metal atoms
donate electrons to the neighboring boron and nitrogen
atoms on the BN sheet. The charge transfer behavior leads
to metal atoms in cationic form and renders extensively
heteropolar bonding between the metal atoms and the
nearest boron and nitrogen atoms. As a consequence, extra
dipole moments are formed, thus resulting in an increase in
the H2 molecule uptake. To evaluate on distribution of the
electrons with energy of the doped BN systems, we present
the density of states (DOSs) of the pure, Pt-doped and Pd-
doped BN sheet, as shown in Fig. 1d. The Fermi level of
Pt-doped BN sheet is near the conduction band maximum
(CBM), as well as Pd-doped BN sheet. It can be found
from the picture that the total DOS near EF is mainly
dominated by the doping metal atom. Furthermore, mag-
netic property of pure h-BN sheet can be modified by such
doping. Both Pt and Pd atoms have unfilled d orbitals, the
733
spin-charge analysis shows that there is spin charge on
certain atoms of the Pt- and Pd-doped BN sheet. In
Table 1, we can see that the Pt and Pd atoms can induce
magnetization of 1.95 and 1.04 lB, respectively, while no
magnetism is observed on pure h-BN sheet.
The interaction between H2 molecules and the Pt/Pd-
doped BN sheet is investigated by first-principle optimiz-
ing the geometry of both Pt and Pd adsorption on the top of
the N atom. Our calculation results show that a single Pt
atom can bind up to three H2 molecules. The relaxed
structures of Pt-doped BN with adsorbed H2 molecules are
shown in Fig. 2ac. The energy gain Eb by successive
additions of H2 to the Pt-/Pd-doped BN sheet is calculated
using the following formula Eb = E[doped-BN(H2)n ?
E(H2) - E[doped-BN(H2)n-1], where E[doped-BN(H2)n],
E[doped-BN(H2)n-1], and E(H2), are the total energies for
doped-BN(H2)n, doped-BN(H2)n-1, and H2 molecule,
respectively; n is the number of hydrogen molecules
adsorbed on each metal atom of the system. By definition,
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734 Struct Chem (2015) 26:731738

Table 1 The hydrogen molecule adsorption energy Eb (eV), bond sheet with adsorbed H2 (e), the magnetic moments of the TM atoms
length between metal (M = Pt and Pd) and BN sheet (A ), bond length (lTM) (lB), and the total magnetic moments of whole system ltotal
of HH (A ), charge transferred (per H2) M/H2 for metal-doped BN (lB)
System No. of H2 Eb MN HH Mulliken lTM ltotal
charge M/H2

Pt-doped 0 2.044 0.25 1.44 1.95

1 1.974 2.227 1.516 0.39/-0.33 1.04 1.99
2 0.733 2.401 2.021 0.30/-0.37, -0.23 0.85 2.10
0.858
3 0.323 3.37 1.976 0.25/-0.32, -0.17 (2) 0.76 2.03
0.861
0.861
Pd-doped 0 2.124 0.17 0.84 1.04
1 1.249 2.151 0.869 0.61/-0.30 0.54 0.97
2 0.373 2.355 0.869 0.65/-0.19 (2) 0.58 0.95
0.853
3 0.492 3.550 0.851 0.50/-0.16 (3) 0.67 0.93
0.853
0.852

Fig. 2 Optimized geometries of

Pt-doped BN sheet with
adsorption a one H2, b two H2,
and c three H2 molecules, Pd-
doped BN sheet with adsorption
of d one H2, e two H2, and
f three H2 molecules. The bond
lengths of HH, PtH, PdH,
NPt, and NPd are shown (A )

positive adsorption energy corresponds to exothermic
adsorption. When the first H2 molecule is adsorbed on Pt-
doped BN, it adsorbs on top of the Pt atom with a binding
energy of 1.974 eV. As shown in Fig. 2a, a partial disso-
ciation of the H2 molecule is observed, whose length is
increased from 0.750 to 1.516 A . Further, the corre-
sponding distance of Pt to the nearest nitrogen atom
. We note that this hydrogen-adsorption
increase to 2.227 A
behavior is similar to that reported previously for the Pt-
doped BN nanotube and Pt-doped carbon nanotube
[38, 39], which the adsorbed hydrogen is in the atomic
form. Compared with the Pt-doped BN sheet in the absence
of H2 molecule, the adsorption of the H2 molecule weakens
the interaction between Pt and BN sheet due to a hybrid-
ization of hydrogen with the d orbitals of the Pt atom by the
latter analysis of projected of density of states (PDOS).
From Table 1, the Pt atom in the case of adsorption of the
H2 molecule carries a positive charge of 0.39 e. It can be
seen that this Pt atom donates electrons to the H2 mole-
cules, and these electrons are forced to occupy the anti-

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Struct Chem (2015) 26:731738
Fig. 3 The projected DOS of Pt-doped BN sheet with (a) one,
(b) two, and (c) three hydrogen molecule adsorbed on Pt atom. The
projected DOS of Pd-doped BN sheet with (d) one, (e) two, and
(f) three hydrogen molecule adsorbed on Pd atom
bonding orbital of the H2 molecule due to the Pauli
exclusion principle. In the case of two molecules adsorbed
on Pt-doped BN sheet, the adsorption energy decreases to
0.733 eV, while the second HH distance in this system
drastically reduced to 0.858 A , as shown in Fig. 2b. To
examine the maximum hydrogen storage capacity, more
hydrogen molecules are added to the Pt-doped BN system.
The binding energy decreases to 0.323 eV for the third H2
molecule. As shown in Fig. 2c, the HH bond lengths of
adsorbed three H2 molecules are 1.976, 0.861, and 0.861 A,
respectively. We placed the fourth H2 at several different
initial locations near the Pt atom, and we found that the
system gets optimized with one hydrogen molecule far
735
away from the Pt atom. Thus, Pt atom can adsorb a max-
imum of three hydrogen molecules. It can be seen in
Table 1, the binding energy per H2 molecule and the
binding strength between the metalhydrogen complex and
the BN sheet decrease as the number of adsorbed H2
molecules is increased.
For the Pd-doped BN sheet, the configurations for the
adsorption of H2 molecules are shown in Fig. 3df. Our
calculations show that the first H2 molecule adsorption on
Pd-doped BN sheet is different to that in Pt-doped BN
sheet. When the first H2 molecule is adsorbed on the
optimized Pd-doped BN, the adsorption energy is
1.249 eV. As shown in Fig. 2d, the H2 molecule is not
dissociated with HH bond lengths of 0.869 A and the Pt
N distance is 2.152 A. Compared with the case of Pt-doped
BN sheet in the absence of a H2 molecule, the amount of
charge transferred from Pd to BN sheet is reduced, leading
to a weakened interaction between the Pd atom and BN
sheet, and this leads to increased NPd length. When the
second H2 molecule approaches the Pd-doped BN, the
binding energy is calculated to be 0.373 eV with a HH
bond length of 0.853 A . The charge transfer from Pd to BN
sheet decreases upon adsorption of the second H2 mole-
cule; this second H2 molecule further weakens the inter-
action between Pd and BN sheet. When more H2 molecules
are adsorbed on Pd-doped BN, the binding energy for the
third H2 molecule is 0.492 eV. It can be seen in Fig. 2f, the
HH bond lengths of adsorbed three H2 molecules are
0.852, 0.851, and 0.853 A , respectively. Additional studies
show that only three H2 molecules can bind with the Pd
atom. Whats more, it can be seen in Table 1, we find
adatoms on pristine-BN sheet are magnetic.
Hydrogen-adsorption studies over the metal-doped BN
sheet show that both Pt and Pd atoms can adsorb three
hydrogen molecules. For the Pt-doped BN sheet, the first
hydrogen molecule was chemically dissociated, and the
rest of hydrogen molecules are chemically bound to the
metal atom in molecule form, while in the case of Pd-
doped BN sheet, all three hydrogen molecules are chemi-
cally bound and are not dissociated. In Table 1, it can be
seen that the adsorbed H2 molecules carry a negative
charge in metal hydrides and H2 are trapped by Pt and Pd
cation by the charge polarization mechanism [40]. So the
decrease of the adsorption energy with increasing the
number of H2 can be understood. When more than one
hydrogen molecule are adsorbed on the Pt-/Pd-doped BN
sheet, there is effectively less charge transfer from the Pt/
Pd-doped BN sheet to every hydrogen molecules. In order
to understand the nature of binding between the metal atom
and the hydrogen molecules, we depict the PDOS of dec-
orated-BN system with one Pt atom adsorption (a) one,
(b) two, (c) three, and one Pd atom adsorption (d) one,
(e) two, (f) three H2 molecules in Fig. 3. The calculated
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736 Struct Chem (2015) 26:731738

Fig. 4 The difference charge

densities of double-side
adsorption of a Pt atoms and
b Pd atoms. d1 and d2 are the
distance between two Pt/Pd
atoms and the substrates. The
maximum number of hydrogen
molecules adsorbed over the
double-side c Pt-doped BN
sheet, d Pd-doped BN sheet

Fig. 5 The optimized

geometric structures for the two
a Pt atoms and b Pd atoms
adsorption on the same side of
BN sheet, respectively. The
optimized geometric structures
of three hydrogen molecules
adsorption on each c Pt atom
and d Pd atom, respectively

PDOS for Pt- and Pd-doped BN sheet with the first molecule is due to the interaction between the s orbital of
hydrogen molecule are shown in Fig. 3a, d, respectively. It Pt atom and hydrogen molecule. With the number of the
can be seen that the adsorption of the first hydrogen attached H2 increasing, we can see H2 donates partial s

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Struct Chem (2015) 26:731738
electrons to the metal so that H s orbitals are partially
unfilled above the Fermi level. At the same time, metal
donates its electrons back to the anti-bonding r* orbitals of
H2 to form back-donation bonds, and this mechanism is the
so-called Kubas interaction [41]. As shown in Fig. 3, due
to the interaction of H2 molecules, H 1s peaks are broad-
ened and split to two peaks. As more H2 molecules are
adsorbed on metal, the band broadening of the H 1s orbitals
becomes more extraordinary, indicating the H2H2 inter-
action is significant.
To improve the hydrogen storage capacity, the double-
side adsorption of Pt/Pd atoms on BN sheet is also inves-
tigated. We introduced the second metal atom to the other
side of the pristine-BN sheet in order to investigate how
successive Pt/Pd atoms will be distributed. Figure 4 shows
the optimized atomic geometries for two Pt/Pd atoms
adsorbed on the two sides of the BN sheet as well as
hydrogen adsorption. It can be seen that the second isolated
Pt/Pd atom is also preferred to stay on the sit above the N
atom. We noted the distances between two Pt/Pd atoms and
the substrates as d1 and d2, respectively. The d1 and d2 of
the Pt-doped BN system are 2.097 and 2.138 A , which are
slightly shorter than for Pd-doped BN sheet. To gain deeper
insight into the interaction mechanism, the electron charge
density differences for the double-side adsorption of Pt/Pd
atoms are plotted in Fig. 4a, b. It is readily seen that
charges mainly concentrate in the region between metal
and N atom. That is to say, some charges have transferred
from metal atoms to the BN sheet. The results are con-
sistent with the analysis of Mulliken charge in the former.
Therefore, partially charged metal ion and BN sheet would
produce a local electric field that can polarize H2 via the
polarization mechanism. The average binding energy of
metal atom with the BN sheet is calculated using
 
Ea 1=2 EBN 2EM  EBN2M , where E(BN?2M) is
the total energy of fully relaxed adsorption of Pt/Pd atoms
on double-side BN sheet, and E(BN) and E(M) are the
energies of the isolated systems. The average binding
energy of the Pt atom is decreased to 4.484 eV/Pt com-
pared to the value of 5.028 eV/Pt for the case of a single Pt
attachment. The average binding energy with two Pd atoms
are 2.393 eV compared to the value of 4.113 eV/Pd. It
attributes to repulsion between positively charged metal
atoms becomes stronger, thus their average adsorption
energies decrease. We also give the optimized structures of
the maximum number of hydrogen molecules adsorbed
over the double-side, as shown in Fig. 4c, d. It can be seen
that a maximum of three hydrogen molecules are adsorbed
on each metal atom.
Previous studies have shown that doping transition
metal atoms on nano-materials, TM atoms basically prefer
being clustered to being individually dispersed on nano-
737
materials because of the large cohesive energy of bulk TM
[4244]. To verify the possibility of clustering on the Pt-
and Pd-doped BN sheet, we have tested by doping the
second Pt and Pd atom near the metal sites and optimized
the system without any geometrical restrictions. The opti-
mized structures are shown in Fig. 5a, b. The PtPt and
PdPd distances in optimized structures are 2.603 and
2.779 A , which are longer than the values of 2.40 and 2.29
A of Pt2 and Pd2 dimers by LDA approximation calculation
[45]. The bond lengths of NPt and NPd are larger than
those of isolate metal-doped BN sheet. This indicates that
the internal interaction between the two metal atoms due to
the formation of dimer weakens the metal-BN interaction.
To know the hydrogen adsorption on cluster dimmers, we
place three hydrogen molecules on each metal atom and
allow the structure to relax without any geometrical con-
strains. The optimized structures are shown in Fig. 5c, d. It
can be seen in Fig. 5c, there are five hydrogen molecules
around the metal due to the space, while one hydrogen
molecule is far away. In the case of Pd, three hydrogen
molecules are adsorbed upon each Pd atom, while the two
Pd atoms are apart. Thus in both the cases, the overall
amount of chemisorbed hydrogen molecule is reduced
upon decorated-BN sheet due to the clustering.
Conclusions
In summary, the favorable adsorption site of Pt and Pd
atoms doping pure BN sheet and their hydrogen-adsorp-
tion properties are investigated using a first-principle the-
ory. The results show that both Pt and Pd atoms are
preferred to locate on the top of N atom with binding
energies of 5.028 and 4.113 eV, respectively. A strong
chemical bond is formed between the nitrogen and metal
atoms. Both Pt and Pd atoms are capable to adsorb up to
three hydrogen molecules chemically and the metal atom
to BN sheet distance increases with the increase in the
number of hydrogen molecules. It is ideally predicated that
the maximum of gravimetric uptakes are 2.81 and 4.82
wt% of Pt-/Pd-doped BN sheet, respectively, and the
average binding energies per H2 molecule are around
1.010 and 0.705 eV. The binding energies of H2 with
metal-doped BN sheet are in the optimal range for
hydrogen storage H2, and they are higher than that of the
pristine-BN sheet. Unfortunately, the overall amount of
chemisorbed hydrogen molecule is reduced upon deco-
rated-BN sheet due to the TM atoms clustering and not
enough space.
Acknowledgments This work was supported by the National Nat-
ure Science Foundation of China (NSFC. Grant No. 11074176 and
NSAF. Grant No. 10976019).
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738 Struct Chem (2015) 26:731738

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