Hydrogen adsorption on zigzag (8,0) boron

nitride nanotubes
Cite as: J. Chem. Phys. 121, 8481 (2004); https://doi.org/10.1063/1.1799958
Submitted: 26 April 2004 . Accepted: 05 August 2004 . Published Online: 26 October 2004

Xiaojun Wu, Jinlong Yang, J. G. Hou, and Qingshi Zhu

ARTICLES YOU MAY BE INTERESTED IN

Adsorption of hydrogen molecules on the platinum-doped boron nitride nanotubes

The Journal of Chemical Physics 125, 044704 (2006); https://doi.org/10.1063/1.2210933

Defects-enhanced dissociation of on boron nitride nanotubes

The Journal of Chemical Physics 124, 054706 (2006); https://doi.org/10.1063/1.2162897

Boron nitride nanotubes: Pronounced resistance to oxidation

Applied Physics Letters 84, 2430 (2004); https://doi.org/10.1063/1.1667278

J. Chem. Phys. 121, 8481 (2004); https://doi.org/10.1063/1.1799958 121, 8481

© 2004 American Institute of Physics.

JOURNAL OF CHEMICAL PHYSICS VOLUME 121, NUMBER 17 1 NOVEMBER 2004

Hydrogen adsorption on zigzag „8,0… boron nitride nanotubes

Xiaojun Wu, Jinlong Yang,a) J. G. Hou, and Qingshi Zhu
Hefei National Laboratory for Physical Sciences at Microscale, Laboratory of Bond Selective Chemistry
and Structure Research, University of Science and Technology of China, Hefei, Anhui 230026,
People’s Republic of China
共Received 26 April 2004; accepted 5 August 2004兲
The chemical adsorption of H atoms on an 共8,0兲 zigzag boron nitride nanotube is studied using the
density functional theory with the supercell method. One to four H atoms per 32 B and 32 N are
considered. The results show that H atoms prefer to adsorb on the top sites of adjacent B and N
atoms to form an armchair chain along the tube axis. An even-odd oscillation behavior of the
adsorption energy of H atoms on the tube is found, and the average adsorption energy of even H
atoms is obviously bigger than that of odd H atoms. The results can be understood with the frontier
orbital theory. Based on this adsorption behavior, several high-symmetric structures of H adsorbed
boron nitride nanotubes with 50% and 100% coverages are studied. The pairs of lines’ pattern with
50% coverage has the biggest average adsorption energy per H2 among the chosen configurations,
corresponding to ⬃4 wt % hydrogen storage. © 2004 American Institute of Physics.
关DOI: 10.1063/1.1799958兴

I. INTRODUCTION In this paper, we study the adsorption of H atoms on the

Boron nitride 共BN兲 nanotubes, as one kind of materials
with tubular structure, have attracted much research attention
since they were first synthesized shortly after the discovery
of carbon nanotubes.1– 6 BN nanotubes are semiconductors
with a wide gap weakly depending on the diameter, helicity,
or the number of the walls of the tube.1,2 During the growth,
BN nanotubes prefer a nonhelical or zigzag orientation.4 – 6
Recently, experiments were carried out to investigate the hy-
drogen storage in BN nanotubes.7,8 Ma et al.7 studied the
hydrogen adsorption in the capped multiwall and bamboolike
BN nanotubes. They found that the multiwall and bamboo-
like nanotube samples absorb ⬃1.8 and 2.6 wt % hydrogen
under ⬃10 MPa at room temperature, respectively. About
70% adsorbed hydrogen is chemisorbed. Tang et al.8 found
that the defective structures enhance the hydrogen storage
capacity of BN nanotubes up to ⬃4.6 wt %. These investi-
gations indicate that BN nanotubes may be a potential hy-
drogen storage medium. Thus, it is interesting to study the
mechanism of the hydrogen storage in BN nanotubes.
Theoretically, the storage of H2 in BN nanotubes,9 the
adsorption of H atom on the h-BN共001兲 plane10 and on the
outer wall of BN nanotubes11 have been studied. It has been
found that H2 molecule can enter into the BN nanotube
through hexagonal ring and clustering of H2 molecules can
be encapsulated in BN nanotubes. When a single hydrogen
atom chemisorbs on the outer wall of the BN nanotube, the
adsorption is site selective and can be modified by the radial
deformation of the nanotube. However, the chemisorption of
multi-H atoms on BN nanotubes, including the adsorption
behavior and capability of BN nanotubes, has not been stud-
ied.
a兲
Author to whom correspondence should be addressed. Electronic mail:
jlyang@ustc.edu.cn
共8,0兲 BN nanotubes using the density-functional theory
共DFT兲. One to four H atoms per 32 B and 32 N on the outer
wall of the BN nanotube are studied. Our calculations give a
detailed description on the adsorption behavior of H on BN
nanotubes when the number of the adsorbed H atoms in-
creases. Further more, we consider several high-symmetric
configurations of H adsorbed BN nanotubes with 50% and
100% coverages. It is found that the pairs of lines’ pattern
with 50% coverage has the biggest average adsorption en-
ergy per H2 among them, corresponding to ⬃4 wt % hydro-
gen storage.
II. METHOD
Our calculations are carried out using the local-orbital
DFT implemented with the DMol3 package.12 All-electron
calculations are used together with the double numerical plus
polarization basis set12 and the generalized gradient
approximation.13 We use a hexagonal supercell of the size
20⫻20⫻8.64 Å 3 with the length of c equal to twice the
periodicity of the 共8,0兲 BN nanotube 共the minimum distance
between two neighboring tubes is larger than 13 Å兲. 32 B
and 32 N atoms are included in this supercell. The tube axis
is set along the z direction. The Monkhorst-Pack special
k-points scheme14 is used with five k points along the tube
axis. For the high-symmetric structures of H adsorbed BN
nanotubes with 50% and 100% coverages, a small supercell
of the size 20⫻20⫻4.32 Å 3 is used, which contains 16 B
and 16 N atoms.
III. RESULTS AND DISCUSSION
To find the adsorption behavior of multi-H atoms on BN
nanotubes, one to four H atoms per supercell are chemi-
sorbed on the wall of the tube one by one. H atom is put on
the top site of B or N atom. Some possible adsorption geom-

0021-9606/2004/121(17)/8481/5/$22.00 8481 © 2004 American Institute of Physics

8482 J. Chem. Phys., Vol. 121, No. 17, 1 November 2004 Wu et al.

atom on the BN nanotube with and without the radial defor-

mation. The result shows that the adsorption is site selective
and H atom prefers to adsorb on the top site of the B atom
for the undeformed BN nanotube. The adsorption energy is
⫺0.32 eV.
For two H atoms adsorbed on the wall of the tube, we
find that the most stable configuration has the two H atoms
on the top sites of adjacent B and N atoms. The N1-B2
configuration is more favorable than the N1-B7 one. This
indicates that two H atoms prefer to adsorb on the top sites
of two neighboring B and N atoms along the tube axis for
zigzag BN nanotubes. The adsorption energy of two H atoms
on the top sites of two B atoms 共configuration of B2-B6 or
B2-B13兲 is about twice that of the B2 configuration, and
weakly depends on the positions of these two B atoms. The
FIG. 1. Schematic of possible H adsorption sites on a BN 共8,0兲 tube. adsorption of two H atoms on two N atoms is still energeti-
cally unstable. Interestingly, when two H atoms adsorb on B
and N atoms simultaneously 共configuration of N1-B2, N1-
etries are considered, distinguished with the label number of B7, N3-B6, or N14-B2兲, the absolute value of the adsorption
the H-adsorbing B or N atom, shown in Fig. 1. The structures energy is much bigger than that of the adsorption only on B
are optimized with all atoms free. atoms 共configuration of B2-B6 or B2-B13兲 or N atoms 共con-
With the optimized structures, the binding energy of the figuration of N1-N3兲. At the same time, it decreases with the
pure tube (E b 关 BNNT兴 ) and the H adsorbed tube increase of the distance between the H-adsorbing B and N
(E b 关 BNNT⫹Hn 兴 ,n⫽1 – 4) are obtained. The adsorption en- atoms. The relative stability of these configurations
ergy E ads is defined as the difference between them: is N1-B2⬎N1-B7⬎N3-B6⬎N14-B2⬎B2-B13⬇B2-B6
E ads⫽E tot关 BNNH⫹Hn 兴 ⫺E tot关 BNNT兴 ⫺n⫻E tot关 H兴 ⬎N1-N3.
Since two H atoms prefer to adsorb on the adjacent B
⫽E b 关 BNNT⫹Hn 兴 ⫺E b 关 BNNT兴 . 共1兲 and N atoms, the configuration of three H atoms adsorbed on
The results are summarized in Table I. The minus value of the BN nanotube derives from the configurations of N1-B2
E ads indicates that the adsorption is exothermic. In our pre- and N1-B7. The most stable configuration is B7-N1-B2 with
vious work,11 we have studied the adsorption of a single H three H atoms adsorbed on the adjacent B and N atoms along
the armchair direction. The adsorption energy is about
⫺4.48 eV. Other two configurations of B6-N1-B7 and N1-
TABLE I. Adsorption energy, in eV, for 1– 4 H atoms adsorbed on the outer B2-B11 are also possible. Their adsorption energies are
wall of the 共8,0兲 BN nanotube. The adsorption configurations are distin-
guished with the label number of the B or N atoms on which H is adsorbed.
smaller than that of B7-N1-B2 configuration by 0.08 eV. The
configurations of B7-N1-B2, B6-N1-B7 and N1-B2-B11 are
System E ads E ads /H2 more stable than the configurations of N1-B2-N8, N1-B7-
1 H on N1 0.29 0.58 N12, and N1-B2-N12, indicating the third H atom prefers to
1 H on B2 ⫺0.32 ⫺0.64 adsorb on the B atom.
2 H’s on N1-B2 ⫺3.85 ⫺3.85 Based on the configurations of B2-N1-B7, B6-N1-B7,
2 H’s on N1-B7 ⫺3.61 ⫺3.61 and B1-N2-B11, the fourth H atom is adsorbed. The B7-N1-
2 H’s on N3-B6 ⫺3.29 ⫺3.29
B2-N8 and N10-B7-N1-B2 are the most stable configura-
2 H’s on N14-B2 ⫺2.39 ⫺2.39
2 H’s on B2-B6 ⫺0.68 ⫺0.68 tions with the same adsorption energy of ⫺8.20 eV. For
2 H’s on B2-B13 ⫺0.64 ⫺0.64 these two configurations, four H atoms adsorb on the wall of
2 H’s on N1-N3 0.19 0.19 the tube along the armchair direction. In B7-N1-B2-N3 con-
3 H’s on B7-N1-B2 ⫺4.48 ⫺2.99 figuration, four H atoms also form an armchair chain along
3 H’s on N1-B2-N8 ⫺4.26 ⫺2.84
the wall, but this chain is spiral. Thus, these H atoms prefer
3 H’s on B6-N1-B7 ⫺4.40 ⫺2.93
3 H’s on N1-B7-N12 ⫺3.97 ⫺2.65 to form an armchair chain along the tube axis. The configu-
3 H’s on N1-B2-B11 ⫺4.40 ⫺2.93 rations of N1-B2-B6-B7 and B2-N1-N3-N8 are the least
3 H’s on N1-B2-N12 ⫺3.80 ⫺2.53 stable in our chosen models, where the numbers of
4 H’s on B7-N1-B2-N8 ⫺8.20 ⫺4.10 H-adsorbing B and N atoms are not equal.
4 H’s on N1-B2-B11-N12 ⫺6.71 ⫺3.35
4 H’s on B6-N1-B7-N12 ⫺7.06 ⫺3.53
In Fig. 2, the adsorption energy is presented as a func-
4 H’s on B2-N1-B7-N12 ⫺7.74 ⫺3.87 tion of the number of the adsorbed H atoms. The total ad-
4 H’s on B7-N1-B2-N3 ⫺7.75 ⫺3.88 sorption energy and average adsorption energy per H2 of the
4 H’s on N10-B7-N1-B2 ⫺8.20 ⫺4.10 most stable configurations are plotted with square line and
4 H’s on N1-B2-B6-B7 ⫺5.76 ⫺2.88 trigon line, respectively. As shown in Fig. 2, the absolute
4 H’s on N1-B2-N8-B11 ⫺7.75 ⫺3.88
4 H’s on B2-N1-N3-N8 ⫺5.01 ⫺2.50
value of the adsorption energy increases with the increase of
H2 ⫺4.56 the number of H atoms. When the number of the adsorbed H
atoms is even, it increases sharply. Otherwise, it increases
J. Chem. Phys., Vol. 121, No. 17, 1 November 2004
FIG. 2. The total adsorption energy and average adsorption energy per H2 of
the most stable configurations are plotted as the number of the adsorbed H
atoms with square line and trigon line, respectively.
slowly. At the same time, the absolute value of the average
adsorption energy increases in an oscillatory way. Even num-
ber of the adsorbed H atoms gives larger average adsorption
energy than odd number of H atoms. This result can be ex-
plained with the degradation of ␲ bonds in the BN nano-
tubes. For odd and odd⫹1 number of the adsorbed H atoms,
the numbers of destroyed ␲ bonds are equal. But for the
latter, the new N–H bond gives a large contribution to the
sharp increase of the adsorption energy.
Considering the above results, we find a general adsorp-
tion behavior for H atoms on BN nanotubes:
共1兲 H atoms prefer to adsorb on the top sites of adjacent
B and N atoms along the tube axis and form an armchair
chain along the tube axis for zigzag BN nanotubes.
共2兲 When the number of the adsorbed H atoms is even,
the favorable adsorption configuration is that the numbers of
H-adsorbing B and N atoms are equal.
共3兲 When the number of the adsorbed H atoms is odd,
the favorable adsorption configuration is that the number of
H-adsorbing B atoms equals the number of H-adsorbing N
atoms plus one.
共4兲 Even number of the adsorbed H atoms gives larger
average adsorption energy than odd number of H.
To understand this adsorption behavior, we present an
explanation based on the frontier orbital theory. When a H
atom chemisorbs on the BN nanotube, the highest occupied
molecular orbital of H interacts with the lowest unoccupied
molecular orbital 共LUMO兲 of the BN nanotube. It is found
that the LUMO of the pure tube, shown in Fig. 3共a兲, is
mostly contributed by the B atoms. This is the reason why a
single H atom adsorbs on the top site of B atom, instead of N
atom. Figure 3共b兲 is the LUMO profile of the H adsorbed BN
tube with the B2 configuration. The most contribution of the
LUMO comes from the N atoms, especially the N atoms
neighboring the H-adsorbing B atom, such as N1, N3, and
N8. As a result, when the second H atom chemisorbs on the
BN nanotube, the favorable configuration is the adsorption
on the adjacent B and N atoms. And the adsorption on B and
N atoms simultaneously is more favorable than only on B or
Hydrogen adsorption on boron nitride nanotubes 8483
FIG. 3. The LUMO profiles of the pure and H adsorbed BN nanotubes. 共a兲
The LUMO profile of the pure BN nanotube. 共b兲 The LUMO profile of the
B2 configuration. 共c兲 The LUMO profile of the N1-B2 configuration. 共d兲
The LUMO profile of the B7-N1-B2 configuration.
N atoms. Figure 3共c兲 is the LUMO profile of H adsorbed
nanotube with the N1-B2 configuration. The contribution
mainly comes from the neighboring B atoms 共B6 and B7兲.
Thus, the most stable configuration is B7-N1-B2, where
three hydrogen atoms adsorb on the adjacent B and N atoms
along the armchair direction. At last, Fig. 3共d兲 gives the
LUMO profile of the B7-N1-B2 configuration, where the
fourth hydrogen atom will adsorb on the adjacent N atoms
labeled with N8 and N10. And the most favorable configu-
rations with four adsorbed H atoms are N10-B7-N1-B2 and
B7-N1-B2-N8. H atoms adsorb on the adjacent B and N
atoms along the tube axis and form an armchair chain.
The band structures of the pure and H adsorbed BN
tubes are calculated, shown in Fig. 4. Spin up and spin down
electronic structures are distinguished with plus and minus
signs, respectively. For the tube with even number of H at-
oms, the impurity states lie deeply below the valence band
edge 共VBE兲 and the band gap is similar with that of the pure
BN nanotube. For the tube with odd number of H atoms, the
impurity states appear near the VBE, and one of them is
unoccupied. This results in a very small band gap.
Based on the above results, we consider several high-
symmetric geometries of H adsorbed BN nanotubes with
50% and 100% coverages. In previous work, Bauschlicher15
and Froudakis16 have used QM/MM method to study the
hydrogen storage in carbon nanotubes, where they used an
end-saturated carbon nanotube to simulate the infinite tube.
Here, the supercell method is used to study the storage capa-
bility of BN nanotubes, which is convenient to simulate the
infinite H adsorbed BN nanotubes with high coverage and
symmetry. To show the adsorption structures clearly, we re-
peat the unit cell in c direction up to quadruple periodicity,
shown in Fig. 5. For 50% coverage, we consider five iso-
8484 J. Chem. Phys., Vol. 121, No. 17, 1 November 2004 Wu et al.

FIG. 4. Band structures of 共a兲, 共b兲 pure

BN nanotube and H adsorbed BN
nanotubes with the 共c兲, 共d兲 B2, 共e兲, 共f兲
N1–B2, 共g兲, 共h兲 B7–N1–B2, and 共i兲,
共j兲 B7–N1–B2–N8 configurations.
The spin up and down electronic struc-
tures are distinguished with plus and
minus signs, respectively. Fermi en-
ergy level is plotted with dotted line.

mers, namely, 共a兲 the all-boron pattern, where all H atoms

adsorb on the top sites of B atoms, 共b兲 the lines’ pattern,
where hydrogen atoms are parallel to the axis of the tube
with dimer form and evenly spaced around the tube, 共c兲 the
pairs of lines’ pattern, where H atoms are also along the axis
of the tube with the adjacent pairs of lines and form armchair
chains, 共d兲 the rings’ pattern, where H atoms form zigzag
rings with even space, and 共e兲 the pairs of rings’ pattern,
where H atoms form zigzag rings and the rings of hydrogen
atoms are in pairs form. Figures 5共a兲–5共e兲 show these five
isomers. For 100% coverage, all H atoms chemisorb on the
top sites of B and N atoms. The structures are optimized with
all atoms free.
The average adsorption energies per H2 are summarized
in Table II. For the half coverage, the pairs of lines’ pattern is
the most energetically favorable. The average adsorption en-
ergy is about ⫺4.35 eV. This result confirms the above gen-
eral rule on the H adsorption behavior, i.e., H atoms prefer to
adsorb on the adjacent B and N atoms to form an armchair
chain along the tube axis. Although the lines’ pattern has H
atoms adsorbed on the adjacent B and N atoms, the separa-
tion of the adsorption dimers results in the lower stability
than the rings and pairs of rings’ patterns, of which all the
adsorption sites are neighboring. The rings’ pattern is more
favorable than the pairs of rings’ pattern. The all-boron pat-
tern is the least stable because all H atoms adsorb on the top
sites of B atoms.
The above result can also be understood with the hybrid-
ization of B and N atoms in BN nanotubes. Similar with
carbon nanotubes, B and N atoms in pure BN nanotubes are
almost sp2 hybridized. When H atom adsorbs on the top site
of the B or N atom, the H-adsorbing atom is bulged out and
translates from sp2 to sp3 hybridization. This effect can be
found in Figs. 5共a兲–5共e兲. For the pairs of lines’ pattern, one
armchair BN chain is bulged out of the tube and the two
neighboring armchair chains are nearly planar. Thus this con-
figuration has good B–H, N–H bonds and B–N ␲ bonds.
For the lines’ pattern, all B–N ␲ bonds are separated and the
FIG. 5. The optimized structures of high-symmetric H-adsorbing BN nano-
conjugation of the ␲ bonds is destroyed. For the rings and
tubes with 50% coverage.共a兲 is the all-boron pattern. 共b兲 is the lines’ pattern.
pairs of rings’ patterns, the adsorption induces a kind of plus/ 共c兲 is the pairs of lines’ pattern. 共d兲 is the rings’ pattern and 共e兲 is the pairs of
minus changing of the tube diameter to form good B–H and rings’ pattern.
J. Chem. Phys., Vol. 121, No. 17, 1 November 2004
TABLE II. Average adsorption energy per H2 , in eV, for 50% and 100%
coverages.
System E ads /H2
50% all-boron ⫺1.04
50% lines ⫺3.52
50% pairs of lines ⫺4.35
50% rings ⫺3.66
50% pairs of rings ⫺3.63
100% full coverage ⫺3.68
N–H bonds, and the former has the better configuration than
the latter.
The average adsorption energy of full coverage situation
is also obtained and we find that this value is significantly
smaller than that of the pairs of lines’ pattern with 50% cov-
erage. For the 100% coverage, all boron and nitrogen atoms
are bulged out and still form a good tube structure. This
results in a bad configuration to form B–H and N–H bonds.
Considering the bond energy of H2 共the bond energy of H2 is
⫺4.56 eV at this level of theory兲, it is clear that the forma-
tion of 100% coverage will be a very endothermic process
starting with H2 and BN nanotubes. The computed average
adsorption energy of the pairs of lines’ pattern with 50%
coverage is smaller than the bond energy of H2 by 0.21 eV
共about 4.84 Kcal/mol兲. It is possible to achieve this level of
coverage in a slightly endothermic process. The 50% cover-
age corresponds to about 4 wt % H storage. We must point
out, however, that one cannot compare directly this value
with the experiment results. The experiments measured the H
storage in bulk materials with complex structures, where hy-
drogen can exist as either atomic hydrogen or molecular hy-
drogen. They can physically or chemically adsorb in tubes,
on tubes, and in the interstitial regions. Here, only the atomic
hydrogen adsorption is studied and the 4 wt % is the calcu-
lated atomic hydrogen adsorption capacity of single-wall BN
nanotubes. We believe the computed storage capability can
be enhanced if the adsorption of molecular hydrogen is con-
sidered. As for how the molecular hydrogen turns into
atomic hydrogens in the BN nanotube materials, it needs
further theoretical efforts, and is beyond the scope of this
work.
At last, the band structures of H-adsorbing BN nano-
tubes are calculated, which are not shown here. For our cho-
sen configurations, the number of adsorbed H atoms is even
in a supercell. The calculated band structures show that these
configurations have a similar band gap with pure BN nano-
tubes, which indicates that the adsorbed BN nanotubes with
even number of adsorbed H atoms are still semiconductors.
IV. CONCLUSIONS
In conclusion, the storage of H atoms on an 共8,0兲 zigzag
BN nanotube has been studied using the DFT with the su-
Hydrogen adsorption on boron nitride nanotubes 8485
percell method. H atoms prefer to adsorb on the adjacent B
and N atoms to form an armchair chain along the tube axis.
An even-odd oscillation behavior of the adsorption energy of
the H atoms on the tube is found, and the average adsorption
energy of even H atoms is bigger than that of odd H atoms.
For even adsorbed H atoms, the most stable configuration of
the H adsorbed nanotube has the equal numbers of
H-adsorbing B and N atoms. For odd number of adsorbed H
atoms, the most favorable configuration is that the number of
H-adsorbing B atoms prefers to equal the number of
H-adsorbing N atoms plus 1. The calculated electronic band
structures show that the tube with odd number of adsorbed H
has a small band gap because of the impurity states near the
VBE. For the tube with even number of adsorbed H atoms,
the impurity states lie deeply below the VBE and the band
gap is similar with that of the pure tube. For high-symmetric
adsorption configurations with 50% and 100% coverages, the
pairs of lines’ pattern with 50% coverage is the most ener-
getically stable among our chosen models, corresponding
about 4 wt % hydrogen storage, and the adsorbed BN nano-
tubes with the pairs of lines’ pattern are still semiconductors.
ACKNOWLEDGMENTS
This work was partially supported by the National
Project for the Development of Key Fundamental Sciences
in China 共on Grant Nos. G1999075305 and G2001CB3095兲,
by the National Natural Science Foundation of China 共Grant
Nos. 50121202, 20025309, and 10074058兲, by the Founda-
tion of Ministry of Education of China, by the ICTS, CAS,
and by USTC-HP HPC project.
1
A. Rubio, J. L. Corkill, and M. L. Cohen, Phys. Rev. B 49, 5081 共1994兲.
2
E. Bengu and L. D. Marks, Phys. Rev. Lett. 86, 2385 共2001兲.
3
H. J. Xiang, J. L. Yang, J. G. Hou, and Q. S. Zhu, Phys. Rev. B 68, 035427
共2003兲.
4
A. Loiseau, F. Willaime, N. Demoncy, G. Hug, and H. Pascard, Phys. Rev.
Lett. 76, 4737 共1996兲.
5
M. Menon and D. Srivastava, Chem. Phys. Lett. 307, 407 共1999兲.
6
R. S. Lee, J. Gavillet, M. L. de la Chapelle, A. Loiseau, J. L. Cochon, D.
Pigache, J. Thibault, and F. Willaime, Phys. Rev. B 64, 121405共R兲 共2001兲.
7
R. Ma, Y. Bando, H. W. Zhu, T. Sato, C. Xu, and D. Wu, J. Am. Chem.
Soc. 124, 7672 共2002兲.
8
C. C. Tang, Y. Bando, X. X. Ding, S. R. Qi, and D. Golberg, J. Am. Chem.
Soc. 124, 14550 共2002兲.
9
R. E. Barajas-Barraza and R. A. Guirado-López, Phys. Rev. B 66, 155426
共2002兲; T. Oku, Physica B 323, 357 共2002兲.
10
B. Mårlid, K. Larsson, and J.-O. Carlsson, Phys. Rev. B 60, 16065 共1999兲;
J. Phys. Chem. B 103, 7637 共1999兲.
11
X. J. Wu, J. L. Yang, J. G. Hou, and Q. S. Zhu, Phys. Rev. B 69, 153411
共2004兲.
12
B. Delley, J. Chem. Phys. 92, 508 共1990兲; 113, 7756 共2000兲. DMol3 is
available from Accelrys.
13
J. P. Perdew and Y. Wang, Phys. Rev. B 45, 13244 共1992兲.
14
H. J. Monkhorst and J. D. Pack, Phys. Rev. B 13, 5188 共1976兲.
15
C. W. Bauschlicher, Nano Lett. 1, 223 共2001兲.
16
G. E. Froudakis, Nano Lett. 1, 179 共2001兲.