CHAPTER 2.

Tight Binding Calculation of Molecules and Solids

In carbon materials except for diamond, the 11" electrons are va-
lence electrons which are relevant for the transport and other solid
state properties. A tight binding calculation for the 1r electrons is
simple but provides important insights for understanding the elec-
tronic structure of the'll" energy levels or bands for graphite and
graphite-related materials.
2.1 Tight Binding Method for B Crystalline Solid
In this section we explain the tight binding method for a crystalline solid. In the
following sections, we show some examples of energy bands for carbon materials
discussed in the Chapter 1.
!.1.1 Secular Equation
Because of the translational symmetry of the unit cells in the direction of the
lattice vectors, ai, (i = 1,"',3), any wave function of the lattice, lIf, should
satisfy Bloch's theorem
(i=I,,3),
(2.1)
where Til; is a translational operation along the lattice vector ai, and k is the
wave vector[45, 46J. There are many possible functional forms of lit which satisfy
Eq. (2.1). The most commonly used form for 11' is a linear combination of
plane waves. The reason why plane waves are commonly used is that: (1) the
integration of the plane wave wavefunction is easy and can be done analytically,
(2) the numerical accuracy only depends on the number of the plane waves
uaed. However, the plane wave method also has limitations: (1) the scale of the
17
18 CHAPTER 2. TIGHT BINDTNG CALCULATION
computation is large, and (2) it is difficult to relate the plane wave wavefuoclion
to the atomic orbitals in the solid.
Another functional form which satisfies Eq. (2.1) is based on the j-th atomic
orbital in the unit cell (or atom). A tight binding, Bloch function rj is
given by,
_ 1 N ._ _ _
<l>j(k,'1= (j=I,,n). (2.2)
vN A
Here Ii. is the position of the atom and "Pj denotes the atomic wavefunction in
state j. The number of atomic wavefunctions in the unit cell is denoted by fl,
and we have n Bloch functions in the solid for a given k. To form r) in
Eq. (2.2), the 'f'j's in the N (- 10
24
) unit cells are weighted by the phase factor
exp(ik. R) and are then summed over the lattice vectors if of the whole crystal.
The merits of using atomic orbitals in Bloch functions are as follows: (1) the
/lumber of basis functions, n, can be small compared with the number of plane
waves, and (2) we can easily derive the formulae for many physical properties
using this method: Hereafter wecollsider the tight binding functions of Eq. (2.2)
to represent the Block fundions.
It is clear that Eq. (2.2) satisfies Eq. (2.1) since
N
(" -+-) 1" ,'A (- - R-)
A",r a = NL.....e !Pj r+a-
A
.,. 1 .f!-. .'(A-.) (_ (R- _)) (2.3)
e NL.....e !pjr--a
A_.
= e,t.f4t(f T'
J ,'1>
where we use the periodic boundary condition for the M =- N-
1
/
3
unit vectors
in each Go direction,
<l>j(k,f+Mii;) = <l>j(k,'1 (i= 1,.3), (2.4)
consistent with the boundary condition imposed on the translation vector TM.f; =
I. From this boundary condition, the phase factor appearing in Eq. (2.2) satis-
fies exp{ikMa,} = 1, from which the wave number k is related by the integer
-The fun.i14t.ions of the mabod are that.: (1) th_ it: no umple rule to improve
the nwnerical accuracy and (2) atomic ori>itaJ.. do not. deKribe the interatomic repon.
2.1. TIGHT BINDlNG METHOD FOR A CRYSTALLINE SOLID 19
p,
k= 2,.,., (p=O,I ..... M-I), (i=I, ... ,3).
MOi
(2.5)
In three dimensions, the waveved.or r is defined for the z, y and z directions,
as .1:%. k, and Thus M
3
= N wave vectors exist in the first Brillouin zone,
where the .1:; CaD be considered as continuum variables.
The eigenfunctions in the solid j(r, r') (j = I, . ",0), where n is the number
of Bloch wavefunctions, are expressed by a linear combination of Bloch functions
.i'(k, r) as follows:

"';(k, '1 = L: C;;o(k)",;-<k. '1.

;'=1
(2.6)
where Cjj.(r) are coefficienLs to be determined. Since the functions 'i'j(f. r')
should also satisfy Bloch's theorem, the summation in Eq. (2.6) is taken only
for tbe Bloch orbitals i) with the same value of f.
The j-th eigenvalue Ej(k) (j = I", " n) as a function of f is given by
(2.7)
where 1{. is the Hamiltonian of the solid. Substituting Eq. (2.6) into Eq. (2.1)
and making a change of subscripts, we obtain the following equation,

L: Ci;Cw("';11I1"'r} L: 1I;;,(k)Ci;Cw
E;(k) =jj':l ==
L: Ci;Cw{"';I"'r} L: S;;o(k)Ci;C;;,
jj'=l jj'=l
(2.6)
where the integrals over the Bloch orbitals, 7ijj'(k) and SU,(k) are called transfer
integral matrices and overlap integral matrices, respectively, which are defined
by
11;;4) = ("';1111"';')' Sir(k) = ("';1"';') U.i' = 1... ). (2.9)
When we fix the values of the n x n matrices 1f.jj,(k) and Sjj'(k) in Eq. (2.9)
for a given k value, the coefficient Ctj is optimized so as to minimize E;(k).
20
CHAPTER 2. TIGHT BINDING CALCULATION
It is noted that the coefficient Gi
j
is also a function of k, and therefore Cij is
determined for each k. When we take a partial derivative for Cij while fixing
the other Gil', Ci
r
I and C
i
; coefficients, r we obtain zero for the local minimum
condition as follows,
N
L 1/;;'(k)Cw
j'=l
N
L Sji(k)c;jCW
jJ'=1
N
" 1/. ,(k)C7.C,
L..J 11 ,,'J N
iJ'-1 "'-
-!-"-='--------,-" L S;p(k)CW = o.
~ S;P(k1Ci;C
W
) p=.
(2.10)
(2.11)
N
When we multiply both sides of Eq. (2.10) by L:: Sjj'(k)CiJCjj' and llubstitute
jJ'=1
the expression for E;(k) of Eq. (2.8) into the second term of Eq. (2.10), we obtain
N N
L 1/;;,(k)CW = E,(k) L S;;,(k)C
W

;'=1 ;'=1
Defining a column vector,
Eq. (2.11) is expressed by
1/C, = E,(k)SC,.
(2.12)
(2.13)
Transposing the right hand side of Eq. (2.13) to the len, we obtain (1l -
E;(k)S]C; = O. If the inverse of the matrix [1t - E;(k)S] exists, we multi-
ply both sides by [1 - Ej(k)Sj-l to obt.ain Ci = 0 (where 0 denot.es t.he null
vector), which means that. no wavefunct.ion is obt.ained. Thus t.he eigenfunc-
tion is given only when the inverse mat.rix does Dot exist, consistent with t.he
condit.ion given by
d.,[1/ - ESJ =0, (2.14)
where Eq. (2.14) is called t.he secular equat.ion, and is an equation of degree
n, wh06e solution gives all n eigenvalues of E;(k) (i = l,n) for a given k.
'Since G;J i. senerally .. complu: yari.t>le .ith two devea or freedom, .. raJ and .. complex
pan, both GiJ and C:
j
e&ll be yaried independe:nlJ,..
2.1. TIGHT BINDING METIIOD FOR A CRYSTALLINE SOLID 21
Using the expression for E;(k) in Eqs. (2.7) and (2.1l), the coefficients C; as a
function of k are determined. In order to obtain the r ~ dispersion relations
(or energy bands) E
o
(;;), we solve the secular equation Eq. (2.14), for a number
of high symmetry k points.
t.l.t Procedure for obtaining the ener" di"persion
In the "ight binding method, the one-electron r ~ eigenvalues E;(k) are ob-
tained by solving tbe secular equation Eq. (2.14). The eigenvalues E;(k) are
a periodic function in the reciprocal lattice, which can be described within the
first Brillouin zone. In a two or three dimensional solid, it is difficult to show
the energy dispersion relations over the whole range of f values, and thus we
plot E;(f) along the high symmetry directions in the Brillouin 'tone. The actual
procedure of the tight binding calculation is as follows:
1. Specify the unit cell and the unit vectors, ii;. Specify the coordinates of
the atoms in the unit cell and select n atomic orbitals which are considered
in the calculation.
2. Specify the Brillouin zone and the reciprocal lattice vectors, h
j
Select the
high symmetry directions in the Brillouin zone, and k points along the
high symmetry axes.
3. For the selected k points, calculate the transfer and the overlap matrix
element.,7-l;j and Sij."
4. For the selected k points, solve the secular equation, Eq. (2.14) and obtain
the eigenvalues E
i
( k) (i = I," " n) and the coefficients Cu(f).
Tigb.... binding calculations are not self-consistent calculations in which the
occupation of an electron in an energy band would be determined. self-consistently.
That is, for given electron occupation, the potential of tbe Hamiltonian is cal-
culated, from which the updated electron occupation is determined using, for
example, Mulliken's gross population analysis [47]. When the input and the
output of occupation of the electron are equal to each other within the desired
accuracy, the eigenvalues are said to have been obtained self-consisLeDtiy.
When only the tI'alUler matrix is calculated and the overlap matrix is taken .. the unit matrix,
then \he Slater-KOlter extrapolalion aeme ",ulta.
22
CHAPTER 2. T1GHT BINDING CALCULATION
: ':
,
i 7 !7
, .
: C : c
, )(A)'-!B))' " /
c: c: c
I! I ~ I
H ~ H! H
:. .:
Fig. 2.1: The unit cell of traM-
polyacelylene bounded by a box
defined by t.he dot.ted lines, and
sbowin& two inequivalent carhon
atoms, A and H, in the unit cell.
in applying these calculational approaches to real systems, the symmetry of
the problem is considered in detaiJ on the basis of a tight.-binding approach and
the transfer and the overlap matrix elements are onen treated as parameters se-
lected to reproduce the band structure of the solid obtained either experimentally
or from first principles calculations. Both extrapolation methods sucb as k p
perturbation theory or interpolation methods using the Sialer-Koster approach
are commonly employed for carhon-related systems such as a 20 graphene sheet
or 3D graphite [9].
2.2 Electronic Structure of Polyacetylene
A simple example of'll'-energy bands ror a one-dimensional carbon chain is poly
acetylene (see Sect. 1.2.2). In Fig. 2.1 we show, within the box defined by the
dotted lines, the unit cell ror trnns.polyacetylene (CII)... which contains two in
equivalent carbon atoms, A and B, in the unit cell. As discussed in Sect. 1.2.2,
there is one r-electron per carbon atom, thus giving rise to two 'lI'energy bands
called bonding and anti-bonding 1I"-bands in the first Brillouin zone.
The lattice unit vector and the reciprocal lattice vector or this one-dimensional
molecule are given by al = (0,0,0) and hI = (0/211',0,0), respectively. The Bril-
louin zone is the line segment -0/11" < k < air. The Bloch orbitals consisting
or A and B atoms are given by
"j(r) = ;.. L: , R ~ j r - 11,,), (0 =A, B)
vN R..
(2.1')
where the summation is taken over the atom site coordinate Ro for the A or B
2.2. ELECTRONIC STRUCTURE OF POLYACETYLENE 23
(2.17)
carbon atoms in the solid.
The (2 x 2) mat.rix Hamiltonian, 1(,0" (a,p =- A,B) is obtained by 8ubsti--
Eq. (2.15) into Eq. (2.9). When a =- P=- A,
'X(r) = L ,"(R-R'l(IP.(r - R')I'XIIP.(r - R
RR'
t <" L ,""(IP.(r - R')I'XIIP.(r - R
R=R' R=R'to (2.16)
+(terms equal to or more distant than R =- Fe 20)
l2" +(terms equal to or more distant than R =- R! a).
In Eq. (2.16) the maximum contribution to the matrix element ll
AA
comes from
R =- R
I
, and this gives the orbital energy of the 2p level, (2p" The next order
contribution to 1iA
A
comes from terms in R =- R! a, which will be negleded for
simplicity. Similarly, 1i.BB also gives lZp for the same order of approximation.
Next let us consider the matrix element 'HAB(r). The largest contribution
to 'HAB(r) arises when atoms A and B are nearest neighbors. Thus, in the
summation over R!, we only consider the cases Fe :; R a/2 and neglect more
distant terms to obtain
'X(r) = L {'''''(IP.(r - R)I1iIIP.(r - R - 0/2
R
+ ,-;""(IP.(r - R)I1iIIP.(r - R+ 0/2}
2. '06(ko/2)
where t.he t.ransfer integral t is t.he integral appearing in Eq. (2.17) and denoted
by!.
(2.18)
It is stressed that t has a negative value. The matrix element 1is
A
(r) is obtained
from 1lAs(r) through the nermitian conjugation relation 'lto
A
:::: ?lAD' but since
'HAS is real, we obtain 1t.BA :::: 1lAB.
Note that (2" i. not .imply the energy value for the free atom, becauM: the HlUlliltonilln
eontaina a cry.tal potential.
tHere ....e M8umed that all the :It bonding orbit.aI. are equal (l.SA bond.). In the real
(CH):r compound, bond alternation occurs, in .... hich the bond energy alternate. betwe.m 1.7A
and 1.3A bond_, and the two atomic intep-",iODA in Eq. (2.17) are not equal. AlthouYt the
m.tortion of LIle lattice lowen the entT!Y, Lhe electronic enersy alway_ decreues more than
the Iattioe energy in a one-dimension.:! material, and th.... the lattia become. deformed by a
procea called the Peierl. instability. See detail. in Sect. 11.3.1
CHAPTER 2. TIGHT BINDING CALCULATION
24
4.0
3.0
2.0
~ 1.0
0.0
-1.0
-2.0
-1.0 .0.5 0.0
W.
E
0.5 1.0
Fig. 2.2: The energy dispersion
relation E(k) for polyacetylene
[(CH)zJ, given by Eq. (2.21) with
values for the parameters t =-1
and s =0.2. Curves E+(k) and
E_(k) are called bonding,.. and
antibonding ,... energy bands, re-
spectively, and the plot is given
in units of Itl.
The overlap matrix Sij can be calculated by a similar method as used for
1iij, except that the intra-atomic integral yields the energy for the crystal Hamil-
tonian 1ii;, but the overlap matrix rather yields unity for the case of So;, if
we assume that the atomic wavefunction is normalized, SAA = SHn = 1 and
SAB = SBA = 2scos(kaj2), where s is the overlap integral between the nearest
A and B atoms,
(2.19)
The secular equation for the 2pz orbital of [(CH)z] is given by
I
(2p - E 2(t - sE) cos(kaj2) I
2(t - sE) cos(kaj2) (2p - E
(2.20)
" - E)' - 4(' - ,E)' " ..'(k./2)
0,
yielding the eigenvalues of the energy dispersion relations of Eq. (2.20) given by
E(k) = (2p 2tcos(kaj2), _ ~ < k < ~
1 2scos(ka/2) a a
(2.21)
in which the + sign defines one branch and the - sign defines the other branch,
as shown in Fig. 2.2, where we use values for the parameters, (2p = 0, t = -1,
and s = 0.2. The levels E+ and E_ are degenerate at ka = ,...
E+(k) and E_(k) are called bonding,.. and antibonding 1f. energy bands,
respectively. Since there are two 1f electrons per unit cell, each with a different
2.3. TWO-DIMENSIONAL GRAPHITE
25
Fig. 2.3: (a) The unit cell
and (b) Brillouin zone of two--
dimensional graphite are shown
as the dotted rhombus and the
shaded hexagon, respecti vely. iii,
and bi, (i = 1,2) are unit vec-
tors and reciprocaJ lattice vec-
tors, respectively. Energy disper-
sion relations are obtained along
the perimeter of the dotted tri-
angle connecting the high sym-
metry points, r, K and M.
spin orientation, both electrons occupy the bonding 1f energy band, which makes
the total energy lower than f2p.
2.3 Two-Dimensional Graphite
Graphite is a three-dimensional (3D) layered hexagonal lattice of carbon atoms.
A single layer of graphite, forms a two-dimensional (2D) material, called 2D
graphite or a graphene layer. Even in 3D graphite, the interaction between two
adjacent layers is small compared with intra-layer interactions, since the layer-
layer separation of 3.35A is much larger than nearest-neighbor distance between
two carbon atoms, ac_c=1.42A. Thus the electronic structure of 2D graphite is
a first approximation of that for 3D graphite.
In Fig. 2.3 we show (a) the unit cell and (b) the Brillouin zone of two-
dimensional graphite as a dotted rhombus and shaded hexagon, respectively,
where al and ii
2
are unit vectors in real space, and b
l
and 6
2
are reciprocal
lattice vectors. In the :t, y coordinates shown in the Fig. 2.3, the real space
unit vectors at and ii, of the hexagonal lattice are expressed as
(2.22)
where a = liid = Iii, I = 1.42 x .j3 = 2.46A is the lattice constant of two-
dimensional graphite. Correspondingly the unit vectors 6\ and 6, of the recip--
26
roeal lattice are given by:
CHAPTER 2. TIGHT BINDING CALCULATION
b, 2<)
V3a a
(2.23)
to a lattice constant of 4'11" /...I3a in reciprocal space. The direction
of the unit vectors b
1
and b'l of the reciprocal hexagonal lattice are rotated by
!J0
0
from the unit vectors ill and il
2
of the hexagonal lattice in real space, as
shown in Fig. 2.3. By selecting the first Brillouin zone as the shaded hexagon
shown in Fig. 2.3(b), the highest symmetry is obtained for the Brillouin zone
of 20 graphite. Here we define the three high symmetry points, r, K and M
as the center, the corner, and the center of the edge, respectively. The energy
dispersion relations are calculated for the triangle r M K shown by the dotted
lines in Fig. 2.3(b).
As discussed in Sect. 2.3.2, three (J' bonds for 2D graphite hybridize in a
sp2 configuration, while, and the other 2pz orbital, which is perpendicular to
the graphene plane, makes 11" covalent bonds. In Sect. 2.3.1 we consider only 'II'"
energy bands for 2D graphite, because we know that the 11" energy bands are
covalent and are the most imporlant for determining the solid state properties
of graphite.
2.:1.1 11" Bands of Two-Dimensional Graphite
Two Bloch functions, constructed from atomic orbitals for the two inequivalent
carbon atoms at A and B in Fig. 2.3, provide the basis functions for 2D graphite.
When we consider only nearest-neighbor interactions, then there is only an in-
tegration over a single atom in '1l
A
A and 1f.BB, as is shown in Eq. (2.16), and
thus 'H.
AA
= ?iBB = (2p. For the off-diagonal matrix element 'HAB, we must
consider the three B atoms relative to an A atom, which are
denoted by the vectors and R
3
. We then consider the contribution to
Eq. (2.17) from Hl)i" and R
3
as follows:
(2.24)
'/(k)
2.3. TWO-DIMENSIONAL GRAPHITE 27
where t is given by Eq. (2.18)* and f(k} is a function of the sum of the phase
factors of e
ik
.
Aj
(j = 1,,3). Using the z,y coordinates of Fig. 2.3(a}, f(k} is
given by:
(2.25)
Since f(k} is a complex function, and the Hamiltonian forms a Hermitian ma-
trix, we write 1tBA = 1f.A.B in which denotes the complex conjugate. Us-
ing Eq. (2.25), the overlap integral matrix is given by SAA= SBB =:: 1, and
SAB =:: sf(k) =:: SiJA' Here s has the same definition as in Eq. (2.19), so that
the explicit forms for Jl and S can be written as:
_(", t/(k) _( 1 'f(k)
Jl_ , S_
t/(k)" '" '/(k)" 1
(2.26)
Solving the secular equation det(Jl - ES) =:: 0 and using 1i and S as given in
Eq. (2.26), the eigenvalues E(t) are obtained as a function w(t), k", and k,:
E (k) _ '" tw(k)
g2D - 1 sw(t) ,
(2.27)
where the + signs in the numerator and denominator go together giving the
bonding 11" energy band, and likewise for the - signs, which give the anti-bonding
band, while the function w(t} is given by:
w(k) = VI/(k)I' =
..;3k",a k a k a
1 + 4 cos ---"" -'- +4 cos2 .:.I.: .
2 2 2
(2.28)
In Fig. 2.4, the energy dispersion relations of two-dimensional graphite are
shown throughout the Brillouin zone and the inset shows the energy dispersion
relations along the high symmetry axes along the perimeter of the triangle shown
in Fig. 2.3(b). Here we use the parameters i2p =:: 0, t =:: -3.033eV, and s =:: 0.129
in order to reproduce the first principles calculation of the graphite energy bands
[9,48]. The upper half of the energy dispersion curves describes the
anti-bonding band, and the lower half is the 1I"-energy bonding band. The upper
band and the lower 1r band are degenerate at the K points through which
often use the symbol 'Yo for the nelU'ftt neighbor tranllfer integrl'l. 'Yo i. defined by &
pOIIitive value.
28
CHAPTER 2. TIGHT BINDING CALCULATION
"*
r
r--.---,----,
15.0
>10.0
5.0
"
r M K
K
Fig. 2.4: The energy dispersion relations for 20 graphite are
shown throughout the whole region of the Brillouin zone. The
inset shows the energy dispersion along the high symmetry direc-
tions of the triangle r M K shown ill Fig. 2.3(b) (see text).
the Fermi energy passes. Since there are two 11" electrons per unit ceU, these two
'II" electrons fully occupy the lower 'II" band. Since a detailed calculat.ion of the
density of states shows that the density of states at the Fermi level is zero, two-
dimensional graphite is a zero-gap semiconductor. The existence of a zero gap at
the f( points comes from the symmetry requirement that the two carhon sites A
and B in the hexagonal lattice are equivalent to each other.
f
The existence of a
zero gap at the J( points gives rise to quantum effects in the electronic structure
of carbon nanotubes, as shown in Chapter 3.
When the overlap integral s becomes zero, the "If and 1f" bands become
symmetrical around E =(2p which can be understood from Eq. (2.27). The
energy dispersion relations in the case of s = 0 (Le., in the Slater-Koster scheme)
are commonly used as a simple approximation for the electronic structure of a
graphene layer:
E,>D(k.,k,) =t {I (';") +4M' (k;") r
(2.29)
I If the A and B sites had different atoms such all B and N, the site energy f'lp would be
different for B and N, and therefore the calculated energy dispersion would show an energy
gap between the,.- and,.-' bands.
2.3. TWO-DIMENSIONAL GRAPHITE 29
In this case, the energies have the values of 3t, t and 0, respectively, at the
high symmetry points, r, At and K in the Brillouin zone. Thus the band width
gives 16tl, which is consistent with the three connected 11" bonds. The simple
approximation given by Eq. (2.29) is used in Sect. 4.1.2 to obtain a simple
approximation for the eledronic dispersion relations for carbon nallotubes.
Finally let us consider the (J bands of two-dimensional graphite. There ace three
atomic orbitals of Sp2 covalent bonding per carbon atom, 25, 2p,. and 2py. We
thus have six Bloch orbitals in the 2 atom unit cell, yielding six u bands. We will
calculate these six (j bands using a 6 X 6 Han\iltonian and overlap matrix, and
we will then solve the secular equation for each k point. For the eigenvalues
thus obtained, threeofthe six u bands are bonding u bands which appear below
tbe Fermi energy, and the other three u bands are 8ntibonding u bands above
the Fermi energy.
The calculation of the Hamiltonian and overlap matrix is performed ana.-
lytically, using a small number of parameters. Hereafter we arrange the matrix
elements in accordance with their atomic identity for the free atom: 28
A
, 2P1,
211, 2s
B
, 2P:. Then the matri.x elements coupling the same atoms (for
example A and A) can be expressed by a 3 x 3 small matrix which is a sub-block
of the 6 x 6 matrix. Within the nearest neighbor site approximation given by
Eq. (2.16), the small Hamiltonian and overlap matrices are diagonal matrices as
follows,
'Ii" = SAA = (2.30)
00(2, 001
where (2p is defined by Eq. (2.16) and (2. is the orbital energy of the 28 levels.
The matrix element for the Bloch orbitals between the A and B atoms can
be obtained by taking the components of and 2py in the directions parallel
or perpendicular to the (J bond. in Fig. 2.5, we show how to rotate the 2p,.
atomic orbital and how to obtain the (J and 'If components for the rightmost
SinO!: the planar geometry of grAphite satiJies the even symmetry of the H.vniltonian 'Ii lUId
of '2,s, '2p" and 2p,. upon milTOr !'eRection about the pla.oe, and the odd symmetry of tbe
tI and ,.- enerv bands ean be IoIved ""paratdy, bause matnx demenu of different .ymmdry
types do not couple in the HAmiltonian.
30
CHAPTER 2. TIGHT BINDING CALCULATION
Fig. 2.5: The rotation of
The figure shows bow to projed
the tT and components along
the indicated bond starting with
the 2pa: orbital. This method is
valid only fot p orbitals.

(7)0.
(S) .
Fig. 2.6: The band param-
eters for (T bands. The fOUf
cases from (1) to (4) correspond
to matrix elements having 000-
vanishing values and the remain-
ing fOUf cases from (5) to (8) cor
respond La vanishing matrix ele-
menLs.
boud of this figure. In Fig. 2.5 the waveCunction of 12p.,) is decomposed inlo its
tT and r components as follows:
12p",) =cos'i12P.. >+sin .. ).
(2.31)
This type of decomposition can be used to describe a bond in any general direc-
tion, which is discussed in Sect. 1.2. This procedure is also useful for fullerenes
and carbon nanolubes, when we consider the curvature of their surfaces.
By rotating the 2p., and 2P. orbitals in the directions parallel and perpen-
dicular to the desired bonds, the matrix elements appear in only 8 patterns as
shown in Fig. 2.6, where shaded and not-shaded regions denote positive and neg-
ative amplitudes of tbe wavefunctioDs, respectively. The four cases from (I) to
(4) in Fit;. 2.6 correspond to non-vanishing matrix elements and the remaining
four cases from (5) to (8) correspond to matrix elements which vanish because
of symmetry. The corresponding parameters for both the Hamiltonian and the
overlap matrix elements are shown in Fig. 2.6.
In Figs. 2.7(a) and (b) weshow examples of the matrix elements of (2s
A
1?l12p:)
and (2": respectively, obtained by the methods described above. In
tbe case of Fig. 2.7 (a), there is only one non-vanishing contribution, and this
2.3. TWO-DIMENSIONAL GRAPHITE
31
Fig. 2.7: Examples of the
HamilLonian matrix elements of
(J' orbitals, (a) and
(b) (2P:I1/12.:'). By w,.'ing
the 2p orbitals, we tel. the ma-
trix elements in Eq. (2.32) and
Eq. (2.33), respectively.
(b)
(al
CXJ>
comes from Fig. 2.6 (2). The other pertinent cases of Fig. 2.6 (5) or (6) give
matrix elements that vanish by symmetry. Multiplying the phase factors for the
three nearest neighbor B atoms with the matrix elements, we get the following
result:
(2.32)
Similarly, in the case of Fig. 2.7 (b), the non-zero matrix elements correspond
to the cases of Fig. 2.6 (3) and (4),
= +1t. - JIl(1i
v
+1f")e-iltz/'W3e-il:"a/2 (2.33)
j!(1l" +1i. )e-
i
.l: .... /
2
-.13 sin .
The resulting matrix element in Eq. (2.33) is a pure imaginary. However, the
calculated results for the energy eigenvalues give real values.
When all the matrix elements of the 6 x 6 Hamiltonian and overlap matrices
are calculated in a similar way, the 6 x 6 Hamiltonian matrix is obtained as a
function of I.:r; and kyo For given k points we then calculate the energy dispersion
of the q bands from the secular equation of Eq. (2.14). The results thus obtained
for the calculated q and 'If energy bands are shown in Fig. 2.8. Here we have
used the parameters listed in Table 2.1, yielding a fit of the functional form of
the energy bands imposed by symmetry to the energy values obtained for the
first principles band calculations at the high symmetry points (48].
32
CHAPTER 2. TIGHT HINDING CALCULATION
Fig. 2.8: The energy dispersion
relations for (T and 1( bands of
two-dimensional graphite. Here
we used the pa.ranlet.ers listed in
Table 2.1.
K M
20.0
10.0
5"
...
!;;

0.0
-10.0
G
-20.0
K r
value
0.212
0.102
0.146
0.129
s..
S.,
S.
S" =s
1i.. 6.169
?-l,p -5.580
r(, -5.037
1i. == t -3.033
Table 2.1: Values for t.he coupling parameters for carbon at.oms in the Hamilto-
nian for :II" and (T bands in 2D graphite.
vaJue(eV) S
(-)The value for (2. is given relative La seLLing (2,. = O.
In the absence of more detailed experimental or theoretical information,
these parameters can he used as a first approximatton in describing the matrix
elements for most sp' carbon materials fot which the carbon-carbon distance
is close to that of graphite, 1.42A. Further, if the parameters are only sligbtly
changed, the formulation can be used to describe the sri' diamond system and
sp carbyne materials.
As is shown in Fig. 2.8, the 11" and the two u bands cross each other (i.e., have
different syrrunetries), as do the 11". and the two u bands. However, because
of the different group theoretical symmetries between u and 11" bands, no band
separation occurs at the crossing points. The relative positions of these Cf088ings
are known to be important for: (1) photo-transitions from tT to r bands and
2.3. TWODfMENSIONAL GRAP1lITE 33
from If to (TO bands, which satisfy t.he selection rule for electric dipole transit.ions,
and (2) charge t.ransfer from alkali met.al ions to graphene sheets in graphite
intercalation compounds.
Using t.he basic concepuoftwo-dimensionalt;raphite presented in Chapter 2,
we next discuss the structure and electronic properties or sint;le-wall carbon
nanot.ubes in Chapters 3 and 4, respectively.