Single molecular transistor as a superior gas sensor

S. J. Ray

Citation: Journal of Applied Physics 118, 034303 (2015); doi: 10.1063/1.4926853

View online: http://dx.doi.org/10.1063/1.4926853
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 JOURNAL OF APPLIED PHYSICS 118, 034303 (2015)

Single molecular transistor as a superior gas sensor

S. J. Raya)
Institute of Materials Science, Technische Universit€
at Darmstadt, Alarich-Weiss-Str. 2, Darmstadt 64287,
Germany
(Received 19 May 2015; accepted 4 July 2015; published online 16 July 2015)
Single Molecular Transistor (SMT) is known for its quantised nature of transport which can be
used for sensing purposes. In this work, a SMT device prototype has been proposed for chemical
sensing application, which is sensitive at the single molecular level. The operational methodology
and performance have been investigated using first-principles calculations within a density func-
tional theory framework. The charge stability diagram carries unique signature of the molecule
present within the SMT and this property can be used to detect the presence of an individual mole-
cule from a mixture of different molecules. Details about the possible experimental realisation of
such a device has been discussed. The present approach provides a unique combination of very
simple design with operation, perfect gate-island coupling, large temperature range of operation
C 2015 AIP Publishing LLC.
and extremely high detection sensitivity. V
[http://dx.doi.org/10.1063/1.4926853]

I. INTRODUCTION production procedures. Also, separating a single nanowire/

nanotube is difficult and the use of electron beam lithography
With the increase in global warming and enhanced pres-
technique is very expensive compared to the commonly used
ence of green house gases in the air, gas sensing is in very
mass production techniques.
increasing demand to monitor the air quality, presence of
Here, in this work, a novel detection methodology is pro-
toxic gases, green house elements and air pollutants. The gas
posed for the detection of gas molecules with ultra-sensitive
sensors are usually categorised based on the sensitivity and
detection efficiency, but simple and novel in design. The sen-
selectivity of individual molecules, rate of response and sta-
sor is a single molecular transistor (SMT)14,15 based nanopore
bility of the measured signal with time.1 Semiconductor
and its operation can be explained using the theory of
metal-oxide sensors2 are used widely due to their smaller
Coulomb Blockade. Similar to a single electron transistor
sizes and compatibility with microelectronic fabrication pro-
(SET), the “island” in a SMT is connected between the
cess for mass production. But their higher sensitivities are of-
Source (S) and Drain (D) electrodes via two tunnel barriers
ten counter backed by the larger power consumption arising
on both sides. The charge state or the potential of the island
from the high resistance of the material. Conducting polymer
can be controlled by a gate electrode which controls the trans-
based sensors are useful for their room temperature opera-
port behaviour of the device. In this case, the island is a gas
tions and reproducibility in sensing performances, but their
molecule which enters into the device through the source
lifetimes are significantly limited by the presence of humid-
electrode and can change its position within the channel area,
ity and UV-exposure.3 The sensing performance of polycrys-
surrounded by the gate electrode. The presence of individual
talline ceramic material based sensors are restricted by their
molecules can be realised from their respective charge stabil-
smaller surface to volume ratio as only the areas near the
ity diagrams, which is unique for each molecule.
grain boundaries are effective for gas adsorption.4
In the present case, first-principles based Density func-
In the recent years, low dimensional nanostructures
tional theory (DFT) calculations are performed to investigate
attracted significant attention for gas sensing due to their
the operation and performance of such devices for different
higher surface to volume ratio, which is reflected in their dras-
types (paramagnetic and diamagnetic) of molecules within
tic change of resistances on the adsorption of an alien mole-
it. The charge stability diagram is calculated for individual
cule.5,6 Improvement in the gas sensing capacity was achieved
molecules, a mixture of different types of molecules and for
using one dimensional nanostructures like carbon nanotubes,7
varied concentration of molecules to investigate the behav-
ZnO nano-belts,8 silicon,9 In2O3,10 and SnO211 nanowire based
iour of such SMT. The density of states (DOS) profile and
sensors. More recently, 2D materials like graphene,12 MoS213
charge stability diagrams are used to understand the applic-
and phosphorene are claimed to be very useful for gas sensing
ability of this technique for sensing applications and its mea-
due to their layered structures that allow molecules to adsorb
surement sensitivity.
preferentially on specific lattice sites reaching high detection
sensitivity up to 1 ppb (1 in 109).12 Although these materials
II. COMPUTATIONAL PROCEDURE AND SYSTEM
provide excellent response and recover characteristics, but DESCRIPTION
their applicabilities are mostly limited by the absence of mass
The novel device structure used in the present work is
illustrated in Fig. 1, which is significantly different from the
a)
Electronic mail: ray.sjr@gmail.com conventional single molecular transistor geometry described

0021-8979/2015/118(3)/034303/6/$30.00 118, 034303-1 C 2015 AIP Publishing LLC

V

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 034303-2 S. J. Ray
FIG. 1. Schematic of the SMT device used in the present work: (top) tilted
view, (bottom) cross section of the device taken along the dotted “red” line.
A sample illustration of the orientation of the molecules within the device is
depicted in the cross sectional view.
earlier.14–17 The present device has few strikingly different
features from the conventional SET devices: (a) the Source
(S) and the Drain (D) electrodes are not identical, (b) a larger
coverage of the gate electrode surrounding the entire island
from all different sides which provides better control over
the electrostatics of the island and (c) the position of the
island is not fixed within the channel/pore region. The device
structure can be most simply described as a cylindrical tube
of square aperture with an open and close end. The S/D elec-
trodes are placed at the two ends of the tube and the gate
electrode covers the larger fraction of the area in between
them.
The active component of the device (i.e., the island) is the
gas molecule which is introduced inside through the Source
electrode and stays within the channel area. For a mixture of
gases, the distribution of the gas molecules within the pore
area can be found from the cross sectional view of the SMT in
Fig. 1. Following the axis convention mentioned in Fig. 1, the
S/D electrodes are placed along the yz-plane, while the motion
of the molecule is ideally directed along the x-axis. The
Source electrode has a square cross section of 2 Å thickness
with a pore opening of 8 Å  8 Å area. The drain electrode is
also square shaped, placed at the back of the hollow region
which has an area of 10 Å  10 Å and 2 Å thickness along the
x-direction. The gate electrode covers the central part of the
device which is separated from the S/D electrodes via a dielec-
tric layer of 3 Å thickness at both ends. The thicknesses of the
gate electrode and the dielectric layer placed underneath it
covering the channel region of the device are 5 Å and the
dielectric materials have a dielectric constant of 10 e0 . All the
electrodes are metallic which are considered to be made of
Gold for the present work. Experimental reports on single mo-
lecular devices typically considered alumina as a dielectric
layer (dielectric constant 9  11e0 ), with a typical thickness
between 2 and 5 nm.18–20 The thickness of the dielectric layer
determines the capacitive coupling between the gate and the
molecule. For materials with larger dielectric constants, a
smaller thickness can be used, while for a dielectric layer with
smaller dielectric constant, a larger thickness provides similar
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J. Appl. Phys. 118, 034303 (2015)
capacitive effect. Changing the thickness within a few nm-
regime will only result in a different operational voltage range,
keeping the device operational in a similar manner.
The charging energy of the gas molecule within the SMT
is estimated using DFT calculations based on Non-
Equilibrium Green’s Function (NEGF) formalism, which is
incorporated within the Atomistix Toolkit package.21 In this
pseudo-potential based approach, a compensation charge is
introduced at each atomic sites to screen the electrostatic inter-
actions. The NEGF based approach was developed by several
authors22,23 and was introduced within a SIESTA for non-
equilibrium system by Brandbyge et al.24 Later Kaasbjerg and
Flensberg25 performed similar DFT calculations for the stand-
ard equilibrium case and Stokbro16 had extended this method-
ology within a NEGF-DFT framework of Quantum Wise.21
The self-consistent calculations are performed using the
Generalised Gradient Approximation (GGA) of the Perdew-
Burke-Ernzerhof (PBE)26 exchange-correlation functional
where the wave functions are expanded within a double-f
polarised (DZP) basis set. The metallic electrodes are consid-
ered to be equipotential surfaces and Neumann Boundary con-
ditions are used to solve the Poisson’s equation to account for
the absence of the perpendicular components of the electric
fields from the metallic surfaces. This method has been suc-
cessfully used to estimate the charging energies of different
molecules within the SMT14,16 that have found agreement
with experimental results.
III. RESULTS AND DISCUSSION
In the presence of a gas molecule, the device becomes
operational and 3 different molecules are considered for the
present investigation. The total energy of the CO2 molecule
within the SMT as function of the gate voltage (Vg) is illus-
trated in Fig. 2(a). A part of the total energy is contributed
by the work function of the metallic electrode which for the
present case is: W ¼ 5.28 eV. For a given charge state q, the
total energy varies almost linearly with the gate voltage,
which can be further expanded using the following
equation:14,15,17
Eðq; Vg Þ ¼ E0 ðqÞ þ aqVg þ bðeVg Þ2 ; (1)
where E0 is the zero-term in energy which is independent of
Vg, a is a measure of the strength of the gate-island coupling,
b quantifies the contribution of electrical polarisation in the
present electrostatic environment and e is the single elec-
tronic charge. The values of the coefficients are estimated by
making a least square fit to the DFT calculated energies
which are found to be a ¼ 0.9998 and b ¼ 1e9 eV1. The
almost linear dependence of the total energy with Vg indi-
cates the minimal presence of the polarisation contribution
in the present geometry which is possible due to the larger
coverage of the gate electrode on the island area from all dif-
ferent sides.
The electrostatics and the nature of conduction within a
SMT can be understood in details from the charge stability
diagram, as illustrated in Fig. 2(b). In the weak coupling re-
gime of operation, conduction occurs through the process of
 034303-3 S. J. Ray J. Appl. Phys. 118, 034303 (2015)

FIG. 2. (a) Total energy of the CO2

molecule as function of Vg for different
charge states (q) within the SMT. (b)
Charge stability diagram of the CO2
molecule within the SMT. The colour
bar on the right represents different
change states. (c) Charging energies of
different molecules within the SMT in
various configurations.

sequential tunnelling, when as electron arrives from the from the DOS profile. It is also to be noted that for a given
source electrode to the island and finally moving to the drain molecule, the DOS profile stays invariant for different con-
to complete the conduction path. The tunnelling rate is con- figurations when the molecule is rotated from its initial (pre-
trolled by the coupling strength between the island-S/D elec- sented in this work) configuration. In the current approach, it
trodes and for a larger separation between the S/D electrodes, is also possible to detect the presence of a magnetic moment
the incoming and outgoing states of the electron from the from the Spin DOS (SDOS) profile, as shown in Fig. 3(c) for
island are almost uncorrelated. For a given Source-drain bias NO2. The paramagnetic nature of NO2 can be detected from
(Vd), a line scan along the Vg results in a series of periodic the splitting of the up (") and down (#) energy peaks in the
peaks that indicates the addition/removal of an electron from SDOS. When more than one molecule is present within the
the island. A series of such scans for a symmetric range of Vd SMT, the presence of individual molecules can be identified
result in diamond shaped regions on the Vg  Vd plane. No from their characteristic energy peaks, which for the case of
conduction takes place within each of the diamond regions (i) CO2 are (3rg ; 2ru ), (ii) NH3 is 2a1 , and (iii) for NO2 are
and the charge population changes by 1 between neighbour- (3a1 ; 2b1 ). This behaviour provides a better way of detecting
ing diamonds. The charging energy (Ech) of the island in the the presence of individual gas molecules within the SMT.
neutral state can be estimated from the height of the central The charge stability diagram of a SMT carries signifi-
diamond, which for the case of CO2 is 14.64 eV. The nature cant information about the island properties and for the
of the electrostatics stays almost the same for the case of
other molecules within the SMT and the comparison between
different charge stability diagrams are discussed at a later
part of this article.
The total DOS estimated for individual gas molecules
within the SMT are illustrated in Fig. 3. For each of the mol-
ecules, positions of different molecular orbital energy states
can be identified from respective energy peaks in the DOS
profile. The HOMO and LUMO orbital states can be found
to be placed symmetrically around the Fermi energy (EF) for
all these molecules. It is to be noted in this context that cal-
culations performed using Local Density Approximation
(LDA)27 of the exchange-correlation functional also resulted
in similar electrostatics for these gas molecules within the
SMT. However, individual energy peaks in the DOS profile
are much prominent with GGA as it considers a higher order
approximation than LDA. This is advantageous for the case
of a mixture of different molecules as the overlap of different FIG. 3. Density of states of different gas molecules within the SMT: (a) CO2,
orbital peaks is minimal and signatures of individual mole- (b) NH3 and (c) Spin density of states for the NO2 molecule. Schematics of
cules could be identified from their respective peak positions the respective molecules are presented in the inset of these figures.

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 034303-4 S. J. Ray
present case, unique signature of different molecules could
be identified from it. The presence of different charge states
for different molecules within the SMT can be realised from
the evolution of the different coloured regions on the charge
stability diagram. The charge stability diagram is different
for different molecules within the SMT and this property can
be utilised for detecting the presence of individual molecules
from it. The charge stability diagram for the case of a SMT
with a CO2, NO2 and a NH3 molecule is illustrated in Fig.
4(a). Line scans taken along the dotted arrows are illustrated
in Figs. 4(b) and 4(c). The horizontal line scans taken along
the Vg axis in Fig. 4(b) result in the occurrence of regular
peaks with equal heights. The presence of different mole-
cules could be identified from their respective peak positions,
which is different for different island configurations. When
the island is a single molecule, the first peak in the line scan
around Vg ¼ 0 occurs at a value of Vg, which is much larger
than the Vg value for an island containing more than one
molecule within the SMT. The first peak in Fig. 4(b) near
Vg ¼ 0 is observed when all the 3 molecules are present,
which can be explained as the effective size of the island is
larger in this situation compared to the case of a single mole-
cule and the electrostatic influence of the gate electrode is
also higher. It is worth noting that the separation between
two neighbouring peaks along the Vg axis is determined by
the strength of the gate-island coupling.
In a similar manner, line scans taken along the Vd axis
are plotted in Fig. 4(c) for various island configurations.
Starting from Vd ¼ 0, the charge state of the island can be
changed to an excited state with an increase in Vd. Successive
enhancement in Vd results in moving to the next excited
states, which is symmetric around Vd ¼ 0. This is possible
due to the almost symmetric position of the S/D electrodes
with respect to the island in the SMT. From the q ¼ 0 state,
the occurrence of the 1st excited state can be found at differ-
ent values of Vd for different molecules. This is a measure of
the charging energy (Ech) of the molecule which is highest
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J. Appl. Phys. 118, 034303 (2015)
for CO2 and lowest for the case when all 3 molecules are
present within the SMT, as shown in Fig. 2(c). It is to be
noted that the symmetric occurrence of plateaus around
Vd ¼ 0 is not always possible during an experimental scenario
due to the asymmetry in the S/D electrode structures.
However, the presence of different molecules can be identi-
fied form their respective line scans which are different from
each others and they are also different from the situation of a
mixture of molecules present within the SMT. The additional
energies estimated for various molecular species within the
SMT are much smaller than their gas phase values, and this
reduction is caused by the electrostatic environment sur-
rounding the molecule, leading to a better stability of individ-
ual molecules in the SMT. This suggests the intactness of the
molecules in the presence of non-zero Vg, Vd, which can also
be confirmed from the occurrences of respective molecular
orbital states in the DOS profiles, as presented in Fig. 3.
The proposed device structure is designed aiming for
triggering interests in experimental works. The molecule
will be allowed to enter through the S electrode which can
then travel/stay within the channel region of the device
which is surrounded symmetrically by the gate electrode.
Due to the weak coupling regime of operation, a measurable
current can always be detected as long as a molecule is pres-
ent within the device, which could be realised from the
charge stability diagram. If x is the number of available
charge states in a given bias window, then the current can be
expressed as, I ¼ Cðx  1Þ, where C is a constant that
depends on the coupling strength between the island and the
source-drain electrodes. The capacitance between them can
be used as a measure of this, which can be estimated indi-
rectly from the charge stability diagram. The 3rd axis on the
charge stability diagram represented by the charge state q,
will be replaced by the source-drain current or conductance
which can be measured easily using std. lock-in technique at
various Vd, Vg values. For different molecules, the conduct-
ance pattern on the Vd  Vg plane will be different, similar
FIG. 4. (a) Charge Stability Diagram
of the SMT with CO2, NH3, and NO2
molecules within it, (b) horizontal line
scans taken along the Vg axis (for a
fixed Vd), (c) vertical line scans taken
along the Vd axis (for a fixed Vg) of the
charge stability diagram as indicated
along the dotted lines and (d) dq=dVd
as function of Vd for the zoomed
region of Fig. 4(c).
 034303-5 S. J. Ray
to the case as explained in this work. Various molecules
could be differentiated from their respective charge stability
diagrams or in a way as explained from the line scans taken
along the Vg or Vd axis in Figs. 4(b) and 4(c). Due to the dif-
ferences in the charging energies of different molecules
within the SMT, the peak positions will be different in differ-
ent cases and this could be used for detecting the presence of
individual molecules. In this work, only the presence of indi-
vidual molecules are discussed, which is not the situation in
an experimental case. For the case of more than one mole-
cule of a specific gas, the distribution of different charged
regions on the charge stability diagram stays the same, as the
diagram only gets influenced by the energy levels of the mol-
ecule and not by their numbers. However, for the case of a
larger numbers of molecules, the absolute amplitude of the
current/conductance can be different experimentally. But the
peak positions along the Vg or Vd axis and the sizes and
shapes of the diamonds are expected to stay the same. In this
work, the analysis is done using 3 different molecules, but
this method is generic and applicable for any molecule which
could be used to separate out the presence of an individual
molecular species from a mixture of different molecules.
The dimensions of different components of the device
used for the present work are suitable for performing calcula-
tions within a restricted computing power. The metallic elec-
trodes are considered as equipotential surfaces and the sizes
of the electrodes can be larger than the present values for ex-
perimental fabrication. The device will work in a similar man-
ner for larger dimensions as long as various components
could be scaled appropriately. For a realistic scenario, in the
presence of a certain N numbers of molecules within the chan-
nel region, the effective island size will increase by a factor N,
which will allow the S/D separation and gate-island distance
to increase by a factor dependent on N. Alternatively, an array
of such sensors can be placed together in the form of a matrix,
as shown in Fig. 5, which will speed up the detection process.
For a m  m sized matrix, the effective volume of the channel
region will be enhanced by a factor of m2 and a common S/D
electrode can be used instead of multiple electrodes for all the
FIG. 5. Frontal view of a 4  4 sized matrix of sensors in the xy-plane. The
green coloured region is the common source electrode and the rectangular
shaped boxes are the arrays of channel regions labelled in a (n, n) format,
which work as the entrance to the nanopore.
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J. Appl. Phys. 118, 034303 (2015)
components simultaneously. The passage time of any mole-
cule within the SMT is another important factor to consider,
which can be tuned according to the need by increasing the
channel length. Once the molecule is inside the SMT, it is
forced to stay within the channel region as the Drain is closed
from the other side and this will not allow the molecule to
leave the pore area, which is a genuine advantage of this spe-
cific architecture. Due to the principle of operation of a single
molecular transistor, this device can allow detection sensitiv-
ity at a single molecular level principally, which is signifi-
cantly larger than the sensitivity provided by the presently
available sensors. The charging energies of different gas mol-
ecules are high enough (Ech  kb T300K ) for room temperature
operation and this allows operation over a large temperature
range, which is significantly useful as the combination of
higher sensitivity and elevated temperature of operation pro-
vides unique advantage to this approach.
IV. CONCLUSION
In this work, a SMT nanopore based detection method-
ology is proposed for the sensing of gas molecules. The de-
vice prototype is designed in a such a way to attract
experimental works in this area. The device operation and
performance analysis are performed using DFT based Ab-ini-
tio calculations which revealed that it could work on a broad
range of temperatures around the room temperature, owing
to the high charging energy of the molecules within it. It has
been found that this method can detect the presence of indi-
vidual molecules from a mixture of different molecules with
a maximum sensitivity at the single molecular level. The
charge stability diagram is unique for each molecules and
can be used as a fingerprint for detection from a mixture of
molecules. The flexibility of the region of operation, simple
device design and extremely high detection sensitivity pro-
vide genuine advantage of this methodology over presently
available sensing methods.
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