PHYSICAL REVIEW B

VOLUME 59, NUMBER 3

15 JANUARY 1999-I

Ab initio pseudopotential method for the calculation of conductance in quantum wires

Hyoung Joon Choi and Jisoon Ihm
Department of Physics and Center for Theoretical Physics, Seoul National University, Seoul 151-742, Korea Received 20 July 1998 We develop a method to incorporate the Kleinman-Bylandertype ab initio pseudopotential in the calculation of conductance in quantum wires using the Landauer formalism. This method is computationally efcient and mathematically stable; it does not involve singularity in inverting the transfer matrix. We also describe the ab initio nonlocal pseudopotential method to calculate the complex band structure that is required in the wave-function matching between the resistive material and the realistic metal probe. We present, as an example, the calculated conductance of the (10,10) carbon nanotube with a pentagon-heptagon-pair defect in the low-temperature limit. S0163-18299904703-7

I. INTRODUCTION

Accompanied by the advance in nanostructure fabrication technology, extensive studies on the conductance of quantum wires have been performed recently. Electrons in nanostructures can retain their phase information over a fairly large distance between metallic probes at low temperature and the nanostructures act as electron waveguides of given shapes. In this situation, quantum mechanics is required to describe the behavior of electrons. Theoretical investigations on such systems usually use a scheme of conning potential in a quantum wire,1 the local pseudopotential approach,2 and the Green-function method.3 For an ab initio treatment of the problem, we note that nonlocality in potential is inevitable. Although the Kleinman-Bylander ab initio pseudopotential method has been used in the Car-Parrinello molecular dynamics as well as in the electronic structure calculation of solids, the same ab initio method has not been applied yet to the quantum conductance calculation for actual solids including realistic metal probes. A major difculty here is to deal with the response of the conducting electrons to the nonlocality of the potential, which cannot be determined locally in the multiple scattering process until the full solution is found. We report here that we now overcome the problem by using the same trick of solving inhomogeneous differential equations as used in the Kleinman-Bylandertype pseudopotential electronic structure calculation. Another practical obstacle to the conductance calculation has been the singular behavior of the transfer matrix. For an efcient computation of conductivity, it is desirable to calculate the transfer matrix in a real-space representation and then invert the transfer matrix.4 In this technique, however, numerical errors in the elements of the transfer matrix may blow up exponentially during successive multiplications of transfer matrices and make it difcult to treat large systems. The present method avoids such numerical instability and is not limited by the length of the system. To demonstrate the applicability of our method to a real solid, we will present the calculated conductance of a (10,10) carbon nanotube with a pentagonheptagon-pair defect. Our work is focused on an efcient, but still exact method to calculate the transmission matrix of a large system for a

given nonlocal potential. This method is applied to the calculation of the conductance based on the Landauer formalism. As a prototype of analyzable systems, we consider an atomic-scale wire consisting of a resistive region and two semi-innite metallic leads attached to it as shown in Fig. 1. The resistive region may have any kinds of defects or disorder and the metallic leads have crystalline structures so that their atomic arrangement and potentials are periodic along the z direction. With such a system, we are interested in the computation of the scattering of an electron wave function when it is incident to the resistive region from the left or right metallic lead. The system can be generalized to a wire with more than one resistive region, a junction of two different metallic wires, etc. With the Kleinman-Bylandertype nonlocal pseudopotential in the Hamiltonian, we derive generalized inhomogeneous differential equations from the selfconsistent Kohn-Sham equation. Then we solve the equations with the wave-function-matching method for a given electron energy E . Unfortunately, the mathematical formalism we are going to present in the next section turns out to be rather sophisticated and a lot of bookkeeping is unavoidable. Still, the computational algorithm we have developed is very stable and gives consistently good results. This paper is organized as follows. In Sec. II, we will describe a method to introduce the Kleinman-Bylandertype ab initio pseudopotential to the calculation of quantum conductance within the Landauer formalism and solve the problem step by step. As an application of the method, the conductance of the carbon nanotube with a pentagon-heptagonpair defect is presented in Sec. III, followed by a summary in Sec. IV.

FIG. 1. Schematic geometry of an atomic wire with two metallic probes assumed in the present conductance calculation.

0163-1829/99/593/22679/$15.00

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1999 The American Physical Society

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HYOUNG JOON CHOI AND JISOON IHM II. METHOD OF CALCULATION A. Overview of the method

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A general form of a pseudopotential is V ps V ps ,loc l, VlP l 1

were to simulate truly periodic arrays of wires interacting with each other, k would have real physical signicance. We split Eq. 4 into a system of equations of and C lm : E r and C lm 2 2 r V loc r r 2m
ik R W lm r R C lm Z l e R

where V ps ,loc is the local part of the pseudopotential, V l is the l th component of the nonlocal part of the pseudopotenl m tial, and P l lm lm is the projection operator to an angular momentum state l . Kleinman and Bylander5 suggested a form of a fully nonlocal separable pseudopotential, V KB ps V ps ,loc

lm

0 0 lm V l V l lm 0 0 lm lm V l lm

d 3 r W lm r * r .

where 0 lm s are the wave functions of a pseudoatom. The above pseudopotential can be put into a simpler form: V KB ps V ps ,loc Z l W lm W lm , lm
0 0 lm V l lm

The following trick has been known in nding general solutions of this type of inhomogeneous differential equations. We rst solve Eq. 6 with the assumption that all C lm s are zero. We call such a solution n ( r), and Eq. 6 becomes a homogeneous equation, E n r 2 2 n r V loc r n r , 2m 8

where Z l is the sign of and W lm 0 0 V l 0 / V . We consider an atom-scale lm l lm lm wire of length L in the z direction (0 z L ). For computational convenience, we assume periodic boundary conditions in the transverse directions ( x , y ) with the unit crosssectional area S , that is, the supercell method is employed in the ( x , y ) directions. For a conductance calculation of an isolated wire, we allow a large vacuum region between wires so that interwire tunneling is suppressed and inter-wire interactions are negligible. With such a periodic arrangement of wires in the xy plane and the nonlocal pseudopotential of Eq. 3, the self-consistent Kohn-Sham equation6 reads E r 2 2 r V loc r r 2m
Z l W lm r R

where n indicates linearly independent solutions satisfying the condition n ( r R ) n ( r) e i k R . We solve Eq. 6 again with the assumption that only one of C lm s is one and the other coefcients are zero. Equation 6 becomes an inhomogeneous equation, E lm r 2 2 lm r V loc r lm r 2m
e i k R W lm r R , R

Z l

where lm ( r) is a particular solution for each ( , l , m ) satisfying the condition lm ( r R ) lm ( r) e i k R . The general solution of Eq. 6 becomes

lm R

r a n n r C lm lm r ,
n

lm

10

d 3 r W lm r R * r ,

where is the position of the th atom in the unit supercell, R s are lattice vectors in the xy plane, and V loc( r) is the total screened local potential, which is the sum of local ionic pseudopotentials, the electrostatic potential due to valence electrons, and the exchange-correlation potential within the local-density approximation LDA. From the Bloch theorem ( r R ) ( r) e i k R , we have

where a n s and C lm s will be determined from Eq. 7 and the boundary conditions on planes at z 0 and at z L . Substituting Eq. 10 into Eq. 7, the equations for the coefcients a n s and C lm s have the form C lm
a n d 3 r W lm r * n r n

d 3 r W lm r R * r

l m

C lm

d 3 r W lm r * l m r .

11 5 If Eq. 11 is satised, given by Eq. 10 becomes a solution of Eq. 4. The boundary conditions that determine a n s will be described later. Now, we consider the solution of Eq. 8 for 0 z L in the context of calculating the conductance in the z direction. Because n ( r R ) n ( r) e i k R and there is no periodic conditions imposed along the z direction, we represent n as

e i k R

d 3 r W lm r * r .

In the present situation of periodic arrays of wires far apart, k is merely an artifact of the plane-wave-based supercell method. The result should be and actually is independent of k and we can choose any particular k , say, k 0. If we

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AB INITIO PSEUDOPOTENTIAL METHOD FOR THE . . .

2269

n r n G , z e i k G r ,
G

12

p where ( G ) is the th solution of the following eigenvalue equation in the p th slab,

where G s are the 2D reciprocal lattice vectors in the xy plane. We represent the local potential in the same way, V loc r V loc G , z e i G r . G

p p E G

2 p k G 2 G 2m
p . G V p G G G

13

18

With the wave function and potential in Eqs. 12 and 13, Eq. 8 becomes E n G , z 2 d2 2 k G 2 n G , z 2m dz

p For given E of the incident conducting electrons, k p p p p 2 m ( E E )/ if E E and k i 2 m ( E E )/ if p E E . Normalized eigenfunctions satisfy p p G * G , , G

, z n G ,z . V loc G G
G

19

14

or equivalently, 1 S

To obtain the self-consistently screened local potential in the wire (0 z L ), it is practical to use the supercell method along the z direction with the periodicity L as well as in the xy plane, perform the ordinary plane-wave-based ab initio nonlocal pseudopotential calculation, and obtain V loc( G) for three-dimensional 3D reciprocal lattice vectors Gs. This local potential is now used in Eq. 14 for the scattering situation of the electron of given energy E. In the ordinary method, the fast Fourier transformation FFT is used to calculate the product of the local potential V loc and the wave function in real space. For the purpose of better numerical accuracy, instead of using V loc( G , z ) G z V loc( G) e iG z z in Eq. 14, we employ the following scheme to calculate V loc( G , z ). Let N be the number of real-space grid points along the z direction used in the FFT. We divide the unit cell into N slabs along the z direction and assign a z-independent potential function in each slab, V p ( r ) for the p th slab ( z p 1 z z p ), such that the analytic, not fast, Fourier transformation to momentum space exactly reproduces V loc( G) for all Gs used in the self-consistent calculation, namely, V loc G

p d 2 r r * r , , p

20

where S is the cross sectional area of the system in the xy plane. Let N 2 D be the number of G vectors. To nd the solutions n s for the whole region, it is necessary to deterp p mine N 2 N 2 D coefcients, a n s and b n s. There are N 1 interfaces between N slabs on which the solutions in adjacent slabs join smoothly. This gives ( N 1) 2 N 2 D conditions, with 2 N 2 D degrees of freedom yet to be xed. Therefore, the number of linearly independent solutions of p p Eq. 14 is 2 N 2 D . Details on nding a n s and b n s will be presented in the next subsection. Next, we consider the solution lm of Eq. 9. Because lm ( r R ) lm ( r) e i k R and there is no periodic boundary condition imposed along the z direction, we represent lm as

p1

1 L

zp

e iG z z dz V p G ,

z p1

lm r lm G , z e i k G r .
G

21

15

With lm ( G , z ) above and V p ( G ) in Eq. 15, Eq. 9 in the p th slab becomes

p E lm G , z

where z p pL / N and G z 2 q / L with integer q , N /2 1 q N /2 . V p ( G ) may be regarded as the optimal representative value of V loc( G , z ) for z p 1 z z p obtainable from the set of V loc( G)s. With V p ( G ) obtained by inverting Eq. 15, Eq. 14 in the p th slab becomes
p En G , z

2 d2 p 2 k G 2 lm G , z 2m dz
p ,z V p G G lm G G

2 d2 p 2 k G 2 n G , z 2m dz

i k G Z , l W lm k G , z z e

p n ,z . V p G G G

16

22
in the xy plane where the Fourier transformed value of W lm is given by

p n ( G , z ) can be expressed as p n G , z

p p p p ik p ik zz p1 zzp b G a , ne ne

W lm g , z

1 S

d 2 r W lm r e i g r .

23

17

p The solution lm ( G , z ) is put in the form

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p p p lm G , z G f lm z

HYOUNG JOON CHOI AND JISOON IHM

p p p ik z p b G k a ne n
p p

PRB 59

p p ik z z p 1 ik z z p a b , lm e lm e

24
p where f lm ( z ) is a particular solution of the equation,

p1 p1 p1 p 1 ik G k a n b n e

p1 z

, 28

2 d2 p p p EE f G * lm z Z l 2 m dz 2 G

where z is the thickness ( L / N ) of each slab. Using the p orthonormality of s for a given p, we obtain recurrence relations between the coefcients of the p th and the ( p 1)th slabs,
1 p1 a n 2

W lm e k G , z z

i k G

25

p p1 G * G G

and given by
p f lm z Z l

p1 k k p p1 k

a n e ik z
p

p1 k k p p1 k

b n , 29

p G * e i k G

1 ik p1 b n 2e

p1

zp

z p1

p dz g z z W lm k G , z z

p p1 G * G G

26
p p p with g ( z ) e ik z /(2 ik ) for z 0 and e ik z /(2 ik ) for z p p 0. The coefcients a lm s and b lm s in Eq. 24 are determined from the condition that lm ( G , z ) be smoothly p continuous in 0 z L . Details on nding a lm s and p b lm s will be postponed to the next subsection again. To summarize this subsection, when the nonlocal part of ( g , z ), the local potential V loc( G), the pseudopotential W lm and the energy E are given, we calculate V p ( G ) by invertp p ing Eq. 15, ( G ) from Eq. 18, and f lm ( z ) from Eq. p p 26, construct n from Eq. 17 and lm from Eq. 24, and obtain the solution from Eqs. 10 and 11 and the boundary conditions on z 0 and z L planes to be specied below.
p

p p1 k k p p a n e ik z p1 k

p1 k k p p1 k

b n , 30

or, in the reverse order,

1 ik z p a n 2 e p

p1 p G * G G

p1 p k k p k

p1 a n

p k k p k

p1 p1

b n e ik

p1

, 31

1 p b n 2

p1 p G * G G

B. Computational details: boundary matching

p k k p k

p1 p1 a n

p k k p k

p1 p1

b n e ik

p1

. 32

In this subsection, we explain a method of nding the p p p p coefcients a n and b n in Eq. 17 and a lm and b lm in Eq. 24 from the boundary conditions on the planes between slabs. ( N 1) 2 N 2 D degrees of freedom in the N 2 N 2 D coefcients of n or lm are removed by the ( N 1) 2 N 2 D boundary conditions i.e., both the wave functions and rst derivatives of N 2 D components are continuous between slabs. First, we consider the homogeneous solutions n s. The boundary conditions at z z p are
p p ik z p b G a ne n
p

p1 p1 p 1 ik G a n b n e

p1 z

27

Normally, we calculate n s ( n 1,2,...,N 2 D ) by starting 1 with a 1 n and b n and applying the recurrence relations in N Eqs. 29 and 30 slab after slab until a N n s and b n s are p ik z can be very large for obtained. However, the factors e p p E E because k becomes imaginary, and the summation p of b n in Eqs. 29 and 30 can produce a serious numerical error when the recurrence relation is repeatedly used. We can avoid this blowing up of the round-off errors in the summa1 tion by starting with a 1 n 0 and b n , n and exploiting p p s and b the linearity of Eq. 16 as follows. When a n s are obtained by the recurrence relations in the middle of the computational process, we calculate h nn s that satisfy p n h nn b n , n and make the substitution n n h nn n for n before we use the recurrence relations p again. Because b n , n in the newly dened n s, only

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AB INITIO PSEUDOPOTENTIAL METHOD FOR THE . . .

1 ik p1 b lm 2 e p1

2271

p one term survives in each summation of b n in the recurp1 p1 rence relations for a n s and b n s. We repeat this replacement of n s for every use of the recurrence relations N until a N n s and b n s are obtained. At the nal stage, we N calculate h nn s from b n s and replace n with n s ( n 1,2,..., N 2 D ) have a 1 n h nn n so that n n 0 and b N n , n . Then we calculate the other half of n s ( n N 2 D 1,N 2 D 2,...,,2N 2 D ) by starting with a N n , n N 2 D and b N n 0 and applying Eqs. 31 and 32 slab 1 by slab until a 1 n s and b n s are obtained. Here again, we p1 avoid the summation of a n in the recurrence relations using the same trick of the repeated unitary transformations. With these two sets of recurrence steps, we obtain 2 N 2 D linearly independent solutions n s which are needed to make the general solution of the homogeneous equation. Our method is equivalent to solving Eq. 8 with a basis set of 3D plane-waves and is similar to the well-known modematching technique.7 Now, we consider a method to nd the nonlocal part lm 1 N in Eq. 24 with the condition that a lm 0 and b lm 0. Since

p p1 G * G G

p p1 k k p1 k

a lm e ik z f lm z p
p p p

p1 k k p p1 k

b lm e ik

p1

z p1 f lm z p .

37 While using the above recurrence relations to calculate lm , one should be careful as before because the factors p1 p1 e ik z can be very large for E E so that the summap tion of b lm in Eqs. 36 and 37 can produce a serious 1 1 numerical error again. We start with a lm 0 and b lm 0 and calculate the coefcients slab after slab by means of p p Eqs. 36 and 37. When a lm s and b lm s are obtained by the recurrence relations in the middle of the computap tional process, we calculate h nn s that satisfy n h nn b n p , n and replace lm with lm nn b n lm h nn n bep1 p1 p fore calculating a lm s and b lm s. Because b lm 0 for p all in the new lm , the summation of b lm vanishes p1 when we apply the recurrence relations to obtain a lm s and p1 b lm s. We repeat this replacement of lm for every use of N N the recurrence relations until a lm s and b lm s are obN tained. At the nal stage, we calculate h nn s with b n s and N replace lm with lm nn b n lm h nn n so that lm has 1 N a lm 0 and b lm 0. The calculational loads for solving Eq. 18 and the wavefunction-matching procedure for n and for lm are all proportional to the third power of the number of 2D plane waves p in the 2D basis set ( N 2 D ). Because 2D eigenfunctions p with eigenvalues E much greater than E give negligible contributions to the solution of Eq. 8 with energy E , we can drastically reduce the calculational load by using a small subset of 2D basis functions but still describing the loweigenvalue 2D eigenfunctions very accurately. First, we solve Eq. 18 for all slabs using the 2D plane waves and p p collect the eigenfunctions with eigenvalues E E cut2 D . From the collected eigenfunctions, the basis functions are generated by the Gram-Schmidt orthogonalization. The number of basis functions are determined so that all the collected eigenfunctions are well represented with the new basis functions within the predened criteria. Then, based on the new 2D basis functions, Eq. 18 is transformed to a matrix form in each slab and solved for all eigenvalues and eigenfunctions.
C. Complex band structure of metallic leads

d p f dz lm d p1 f dz lm

zzp

p p ik f lm z p ,

zzp

p1 p1 ik f lm z p ,

33

the boundary conditions at z z p are

p p p p ik z b G a lm e lm f lm z p
p

p1 p1 p 1 ik G a lm b lm e

p1 z

p1 f lm z p ,

34
p p p p p ik z b G k a lm e lm f lm z p
p

p1 p1 G k p1 p 1 ik a lm b lm e
p1

p1 f lm z p .

35

p1 s, we obtain the recurUsing the orthonormality of rence relations between the coefcients of the p th and the ( p 1)th slabs,
1 p1 a lm 2

p p1 G * G G

p1 k k p p1 k

a lm e ik z f lm z p
p p

We assume in this subsection that the potential in a metallic lead is periodic along the z direction with the unit-cell length d and search for solutions of a given eigenvalue E that satisfy

p1 k k p p1 k

p b lm

k G , z d e ikd k G , z .
, 36

38

Since we will use these states only in the region with a boundary, the wave vector k need not be real. With n s and

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HYOUNG JOON CHOI AND JISOON IHM

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d 2 r W lm r * k r

lm s obtained for a unit cell using the method described in previous subsections, k in 0 z d can be expressed as k a n , k n C lm , k lm .
n

C lm , k

lm

39

e ikd

dz

dz

d * k r d 2 r W lm r z

43 When N a atoms having nonlocal pseudopotential with them exist in 0 z d , k in Eq. 39 has 2 N 2 D l nonlocal(2 l 1) N a undetermined coefcients (2 l 1) N a coefcients for each nonlocal l. A bit of caution is necessary in counting N a here. In the ab initio pseudopotential method, the nonlocal terms are nonzero inside some spheres centered at atomic positions. By necessity in the boundary matching procedure explained later, N a is dened here to be the total number of atoms the nonlocal spheres of which share some volume with 0 z d even if the center of the sphere may lie in z 0 or z d . ( N a is typically a very small number compared with N 2 D but we need to count N a precisely to get correct answers. Equation 38 gives boundary conditions for an atom the nonlocal sphere of which is cut by the z d plane. We derive 2 N 2 D l nonlocal(2 l 1) N a algebraic equations by substituting Eq. 38 into Eqs. 40, 41, 42, and 43. We use Eq. 41 only for ( N a N c ) atoms the nonlocal spheres of which completely t inside the region (0 z d ) and we multiply Eq. 42 by e ikd to remove e ikd . Equation 41 for ( N a N c ) atoms does not have the factor e ikd so that the coefcients C lm , k for such atoms are linearly dependent on other coefcients and easily removable from the algebraic equations derived from Eqs. 40, 42, and 43. We can arrange these 2 N 2 D l nonlocal(2 l 1) N c equations into a matrix form AX e ikd BX , where A and B are complex general matrices and X is a column vector containing a n , k s and C lm , k s. We solve this generalized eigenvalue problem using the LAPACK package and obtain eigenvalues e ikd s and corresponding eigenvectors k s. In general, the resulting k is a complex number. States with real k s are propagating modes and those with non-zero imaginary parts are evanescent modes in one direction or another. The propagating and the evanescent modes constitute the complex band structure of the region. The concept of the complex band structure has been studied, say, in the eld of semiconductor superlattices and interested readers may nd more details of the theory in the literature.8 It sufces here to be able to calculate the complex band structure for metals which are to be attached to the left and right of a resistive region. The quantum mechanical probability current I along the z direction for a state is given by I Im

k G , d e ikd k G ,0 ,

G , d e ikd k G ,0 , k

40

where is the derivative of with respect to z . They give 2 N 2 D equations among coefcients in Eq. 39. l nonlocal(2 l 1) N a more equations are necessary to determine a n , k s and C lm , k s, which come from Eq. 11,

C lm , k

d 3 r W lm r * k r .

41

d 2 r r *

r z
dz

Although n s and lm s are dened only inside the region (0 z d ), for atoms whose nonlocal spheres are cut either by the z 0 or z d plane, we need to know k outside as well as inside the region in evaluating integrals in Eq. 11. d is always larger than any diameters of nonlocal spheres. Let N c be the number of atoms the nonlocal spheres of which are cut either by the z 0 or z d plane. In Eq. 11, we extend k outside the unit cell by assuming that k ( G , z ) e ikd k ( G , z d ) for d z 0 and k ( G , z ) e ikd k ( G , z d ) for d z 2 d so that we have C lm , k

2 Z C * lm l lm

z rl

W lm d 2 r r * r ,

44 where r l is the radius of the nonlocal sphere for the angular momemtum l of the th atom.
D. Conductance of real solids with metal probes

e ikd

dz

d 2 r W lm r * k r
d

dz

d * k r d 2 r W lm r z

42 for an atom the nonlocal sphere of which is cut by the z 0 plane and we have

We consider a system consisting of a resistive region that may have any kinds of defects or disorder (0 z L ) and two semi-innite perfect metallic regions attached to the left and right ( z 0 and z L ) of it. For simplicity, we assume that the two semi-innite metals are identical. Generalization to two different metals is straightforward. First, we obtain the complex band structure k of the perfect metallic region and n and lm of the resistive region as described in previous subsections. We now assume that a rightward propagating state k is incident from the left metallic region and there is no incident wave from the right metallic region. The wave function is

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where L and R represent the sets of leftward and rightward propagating states, respectively. When k is complex, k L if its imaginary part is negative and k R if it is positive. When N a atoms exist in the resistive region as dened in the last subsection and nonlocal spheres of N c atoms are cut by the z 0 or z L plane, of Eq. 45 has 4 N 2 D l nonlocal(2 l 1)( N a N c ) undetermined coefcients. Since is smoothly continuous for all z , 4 N 2 D boundary conditions are obtained from two boundary planes, z 0 and z L . Eq. 11 gives l nonlocal(2 l 1) N a conditions. Because Eq. 4 for z 0 and that for 0 z L share those atoms whose nonlocal spheres lie across the z 0 plane, some C lm s for 0 z L are equal to the corresponding nonlocal terms in Eq. 4 for z 0. They give l nonlocal(2 l 1) N c /2 conditions, C lm C lm , k

kL

r kk k ,

z0 0zL zL, 45

a n n C lm lm , n lm
kR

t kk k ,

FIG. 2. Atomic structure of a 10,10 carbon nanotube with a pentagon-heptagon-pair defect. For clarity, atoms around the defect site are marked in solid circles.

terminal measurement.11,12 The issue of dividing the righthand expression in Eq. 49 by some weighted reectance coefcients under different circumstances e.g., nitechannel four-terminal measurement has been studied in the literature11,12 and will not be pursued here.
III. EXAMPLE: CARBON NANOTUBE WITH A PENTAGON-HEPTAGON-PAIR DEFECT

r kk C lm , k , k L

46

where C lm , k is given by Eq. 41 and indicates the atoms whose nonlocal spheres are cut by the z 0 plane. Likewise, Eq. 4 for z L and that for 0 z L share some atoms near z L , which give l nonlocal(2 l 1) N c /2 conditions,

C lm

kR

t kk C lm , k ,

47

where indicates the atoms whose nonlocal spheres are cut by the z L plane. With all these conditions, we construct a set of inhomogeneous linear algebraic equations the number of which is the same as that of the undetermined coefcients in . We solve this set of equations and obtain t kk for all rightward propagating modes k s. The properly normalized transmission coefcient T k of the state k is 1 Ik

T k

kR

I k t kk 2 ,

48

where I k is the probability current per wire of the state k given by Eq. 44 and the summation ( R ) is over the rightward propagating modes not including the evanescent modes. The multichannel generalization of the Landauer conductance formula9,10 is related to T k as G 2e2 T . h kR k

49

This formula is valid in the two-terminal conductance measurement as well as in the many-channel limit of the four-

A carbon nanotube is a new form of graphitic carbon discovered by Iijima13 and draws growing attention due to its potential use as a quantum wire. At low temperature, electrons in the tube seem to retain phase information over a large distance14 and the carbon nanotube acts like an electron waveguide. Using the Kleinman-Bylandertype ab initio pseudopotential, we calculate the quantum-mechanical conductance of an isolated carbon nanotube with a pentagonheptagon-pair defect in the limit of the absolute zero temperature. 10,10-type carbon nanotubes aligned in a hexagonal array in the xy plane with the tube axes along the z direction are considered. The intertube carbon-carbon distance is set to be 6.5 , far enough to mimic isolate nanotubes. A pentagon-heptagon-pair defect is introduced by rotating a CC bond15 and the resistive region consists of six unit cells of the 10,10 nanotube i.e., 14.7 long in the tube axis direction with the defect in the middle as shown in Fig. 2. The length of the resistive region is so determined that it contains the potential modication produced by the defect. In our method, the resistive region need not be extended to cover the modication in the wave function. Atomic positions obtained from the tight binding molecular dynamics16 are used for 240 atoms in the resistive region. We put defectless 10,10 nanotubes to the left and right of the resistive region as metallic leads so that the contact resistance is automatically zero. In order to obtain the selfconsistently screened potential, plane-wave-based selfconsistent calculations using the Kleinman-Bylander pseudopotential are performed for two regions, the resistive region and a unit cell of the defectless tube, respectively. In the self-consistent calculation, the supercell method is used for all three dimensions and plane waves having kinetic energies up to 35 Ry are used to represent the wave function. The screened local potentials V loc( G)s are transformed to

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HYOUNG JOON CHOI AND JISOON IHM

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FIG. 3. Band structure of the defectless 10,10 carbon nanotube. Solid lines are the results of the ordinary plane-wave-based band-structure method and the dots are the propagating mode solutions of the complex band calculation; the two results precisely agree with each other.

FIG. 4. Conductance of the 10,10 carbon nanotube with a pentagon-heptagon-pair defect in solid lines as a function of the incident electron energy. Dashed lines are for the defectless nanotubes.

V p ( G )s using Eq. 15. With an energy cutoff of 35 Ry, 10 slabs along the z direction are enough to represent the shape of the local potential in a unit cell of the defectless tube, and 60 slabs in the resistive region. The slab thickness is 0.246 in both cases. We solve the generalized inhomogeneous differential equation for a unit cell of the semi-innite region and calculate its complex band structure as explained in the last section. The calculated band structure of the defectless tube is shown in Fig. 3. The solid lines are the result of the ordinary 3D plane-wave-based method allowing for a larger cutoff energy along the tube. The points are the propagating modes of our complex band calculation. With E cut2 D being about 0.7 Ry higher than the Fermi energy, the number of 2D basis functions N 2 D is reduced to only one sixth of the number of original 2D plane waves. The two results still agree very well. Next, we solve the equation for the resistive region as explained in Sec. II A. Then we obtain the scattering wave function of the whole wire by joining smoothly the solutions in the resistive region with the propagating and the evanescent modes of the defectless tube at two interfaces respectively. We reemphasize here that, once the selfconsistent potentials in both the resistive and defectless regions are given, no approximation is involved in our formalism and the results are essentially exact. The required memory is about 500 Mbytes and the computing time for the conductance for each energy is about 5 h in a DEC alpha machine. The conductance is obtained near the Fermi level using Eq. 49 and plotted in solid lines in Fig. 4. The dashed lines are the conductance of the perfect nanotube presented for comparison. The single most important result is that the pentagon-heptagon-pair defect does not reduce the conductance of the 10,10 tube at the Fermi level. Although the

charge distribution around the defect changes, both -bonding and -antibonding states at the Fermi level propagate through the defect without deterioration. On the other hand, the pair defect causes two dips in the conductance above and below the Fermi energy. One is at approximately 0.5 eV above the Fermi energy and the other at approximately 0.7 eV below the Fermi energy. The amount of reduction at these dips is 50% of the original value. The dip above the Fermi energy is due to the complete reection of the -bonding state, and the one below the Fermi energy due to the complete reection of the -antibonding state. More extensive results will be presented elsewhere.
IV. SUMMARY

We have described a method to calculate the quantum conductance of an atomic wire. Although our calculational scheme is based on the transfer matrix for the wire, it is compatible with Kleinman-Bylandertype nonlocal pseudopotentials and may be called a truly ab initio method capable of describing practical systems including a real material and metallic leads. The computational algorithm is elaborately designed to be stable despite the fact that we perform, in effect, the inversion of nearly singular matrices in the program. As an example, the conductance of the 10,10 carbon nanotube with a pentagon-heptagon-pair defect is presented as a function of the incident electron energy.
ACKNOWLEDGMENTS

This work was supported by the Korea Science and Engineering Foundation, the BSRI Program of the KRF, and the SRC program of the KOSEF. The computation was carried out using the supercomputer at the SERI.

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