Tight Binding for Graphene

by Sowmya Sathyanarayana Murthy

Tight-binding method - A brief introduction
and

bands of Graphene
TB method with
First nearest neighbours
Second nearest neighbours
Third nearest neighbours
1 Tight-binding method - A brief introduc-
tion:
The basic idea behind the tight-binding method is that the crystal Hamil-
tonian can be approximated by an atomic Hamiltonian when the basis or-
bitals are chosen to be localised. By considering the hopping of the electrons
between the nearest neighbours (atmost the third nearest neighbours), the
bands corresponding to the localised orbitals could be obtained.
Statement of Blochs theorem:
The eigenstates of the one-electron Hamiltonian H = h
2

2
/2m + U(r),
where U(r +

R) = U(r) for all

R in a Bravais lattice, can be chosen to have
the form of a plane wave times a function with the periodicity of the Bravais
lattice:

nk
(r) = e
i

k.r
u
nk
(r) (1)
Where u
nk
(r +

R) = u
nk
(r) for all

R in the Bravais lattice.
In other words, the tight binding method involves the linear combination
of the atomic orbitals located on the various atoms of the crystal, the coef-
cients being the values of the planewaves e
(i

R)
at various positions

R at
which the atoms are located. The atomic states are used as basis orbitals.
If the states are denoted by u
p
(r

R), where p refers to the atomic levels of
atom located at

R, the Bloch functions are given as,
1

p,

k
(r) =
1

R
e
i

R
u
p
(r

R) (2)
and a general Bloch state is a linear combination of the Bloch basis functions
given by

k
(r) =

p
C
p
(

k)
p,

k
(r) (3)
The coecients C
p
(

k) could be obtained by solving the Schrodinger equa-

tion in matrix form:
HC(k) = ESC(k) (4)
The Hamiltonian and the overlap matrix elements could be written as:
H
pq
=
p,k
|H|
q,k
(5)
S
pq
=
p,k
|
q,k
(6)
Where

p,

k
(r) =
1

R
e
i

R
u
p
(r

R)
and
H
pq
=

R
e
i

R
_
d
3
ru
p
(r

R)Hu
q
(r)
S
pq
=

R
e
i

R
_
d
3
ru
p
(r

R)Su
q
(r)
2
2 Structural details of Graphene:
Graphene is a 2D sheet of carbon atoms arranged in a hexagonal pattern, as
shown in Fig. 1. Each carbon atom has 3 nearest neighbours, 6 next-nearest
neighbours and 3 third nearest neighbours.
The unit cell consists of 2 Carbon atoms, labelled as A and B.
1
a
a
2
A
3
R
1
R
2
R
B
Figure 1: Sketch of graphene showing the unit cell (light-blue region) de-
limitated by the two dimensional lattice vectors a
1
= a(

3/2, 1/2) and

a
2
= a(

3/2, 1/2). Lattice constant = a

0
and a =
a
0
3
Vectors R
i
refer
to the rst nearest-neighbour distances.
Carbon atom has 6 electrons and the bonding of the atoms is due to the
overlapping of the orbitals. sp
2
hybridization due to the overlapping of the 2s
orbital with the 2p
x
and 2p
y
orbitals and this is attributed to the structure
of Graphene. The overlap between the p
z
orbitals (that are perpendicular
to the plane) is responsible for the electronic properties of Graphene. The
p
z
orbitals could be almost treated as localized and the overlapping between
the p
z
orbitals gives rise to the bonding and antibonding

bands.
3 and

bands of Graphene
_
H
AA
(

k) H
AB
(

k)
H
BA
(

k) H
BB
(

k)
__

A
(

k)

B
(

k)
_
= E(

k)
_
S
AA
(

k) S
AB
(

k)
S
BA
(

k) S
BB
(

k)
__

A
(

k)

B
(

k)
_
(7)
3
Figure 2: Nearest neighbours B
1i
i=1-3, second nn A
2i
i=1-6, Third
nn B
3i
i=1-3
det
_
H
AA
(

k) E(

k)S
AA
(

k) H
AB
(

k) E(

k)S
AB
(

k)
H
BA
(

k) E(

k)S
BA
(

k) H
BB
(

k) E(

k)S
BB
(

k)
_
= 0 (8)
In order to obtain the energy eigenvalues, the above secular has to be
solved.
Evaluation of the matrix elements
3.1 Taking nearest neighbours only:
For the A Carbon atom, the rst nearest neighbours (or simply the near-
est neighbours) are B atoms, which could be labelled as B
1
,B
2
and B
3
.The
vectors

R
1
,

R
2
,

R
3
connect A atoms to B
1
, B
2
and B
3
respectively. Since
4
Figure 3: Brillouin zone of 2D graphene showing the high symmetry points,
= (0,0),K = (2/

3,-2/3),M=(2/

3,0)
both the atoms of the unit cell are Carbon atoms described by one single p
z
orbital, the following conditions apply:
H
AA
(

k) = H
BB
(

k)
S
AA
(

k) = S
BB
(

k)
H
AB
(

k) = H

BA
(

k)
S
AB
(

k) = S

BA
(

k)
From Eq. 8 it follows:
[H
AA
(

k)E(

k)(S
AA
(

k)][H
BB
(

k))E(

k)S
BB
(

k)][H
AB
(

k)E(

k)S
AB
(

k)][H
BA
(

k)E(

k)S
BA
(

k)] = 0
By suppressing the dependency on (

k) one obtains:
H
2
AA
H
AB
H

AB
2EH
AA
S
AA
+E
2
(S
2
AA
S
AB
S

AB
)+E(S
AB
H

AB
+H
AB
S

AB
) = 0 (9)
Given the denition:
H
AA
S
AA
= E
0
(10)
S
AB
H

AB
+ H
AB
S

AB
= E
1
(11)
H
2
AA
H
AB
H

AB
= E
2
(12)
S
2
AA
S
AB
S

AB
= E
3
(13)
5
Substituting E
0
, E
1
, E
2
, E
3
in 9, a quadratic equation in E is obtained
E
2
2EE
0
+ E
2
E
3
+ EE
1
= 0 (14)
whose solution yields the following dispersion relation:
E

k) =
(E
1
2E
0
) [(E
1
2E
0
)
2
4E
2
E
3
]
1/2
2E
3
(15)
By considering nearest-neigbhor interactions only, the matrix elements
required to evaluate E
0
, E
1
, E
2
and E
3
are obtained in the following way:
H
AA
=
1
N

R
A

R
A

e
i

k(

R
A


R
A
)

A
(r

R
A
|H|
A
(r

R
A
) (16)
where A and A

refer to the same atom-type and N is the number of unit

cells in the crystal.
H
AA
=
1
N

R
A

A
(r

R
A
|H|
A
(r

R
A
) =
2p
(17)
H
AB
=
1
N

R
A

R
B
e
i

k(

R
B

R
A
)

A
(r

R
A
|H|
B
(r

R
B
) =
0
(e
i

R
1
+e
i

R
2
+e
i

R
3
)
(18)
with

0
=
A
(r

R
A
|H|
B
(r

R
A

R
i
) with (i = 1, 2, 3)
H

AB
= H
BA
The same treatment yields the overlap matrix element S
AA
& S
AB
:
S
AA
= 1 (normalization) (19)
S
AB
=
1
N

R
A

R
B
e
i

k(

R
B

R
A
)

A
(r

R
A
|
B
(r

R
B
) = s
0
(e
i

R
1
+e
i

R
2
+e
i

R
3
)
6
(20)
with
s
0
=
A
(r

R
A
)|
B
(r

R
A

R
i
) with (i = 1, 2, 3)
Where

R
i
is the vector pointing from atom A to its nearest neighbours B
i
(see Fig. 1)
Summing up we have:
H
AB
=
0
(e
i

R
1
+ e
i

R
2
+ e
i

R
3
)
S
AB
= s
0
(e
i

R
1
+ e
i

R
2
+ e
i

R
3
)
H
AA
=
2p
S
AA
= 1
H

AB
=
0
(e
i

R
1
+ e
i

R
2
+ e
i

R
3
)
S

AB
= s
0
(e
i

R
1
+ e
i

R
2
+ e
i

R
3
)
Now we insert the Hamiltonian and the overlap matrix elements into the
expression for E

k) that was previously obtained (Eq. 37). E

0
,E
1
,E
2
,E
3
become:
E
0
=
2p
E
1
= S
AB
H

AB
+ H
AB
S

AB
= 2s
0

0
(e
i

R
1
+ e
i

R
2
+ e
i

R
3
)e
i

R
1
+ e
i

R
2
+ e
i

R
3
)
E
2
= H
2
AA
H
AB
H

AB
=
2
2p

2
0
(e
i

R
1
+ e
i

R
2
+ e
i

R
3
)(e
i

R
1
+ e
i

R
2
+ e
i

R
3
)
E
3
= S
2
AA
S
AB
S

AB
= 1 s
2
0
(e
i

R
1
+ e
i

R
2
+ e
i

R
3
)(e
i

R
1
+ e
i

R
2
+ e
i

R
3
)
To evaluate (e
i

R
1
+e
i

R
2
+e
i

R
3
) (e
i

R
1
+e
i

R
2
+e
i

R
3
) we use the
trigonometric relationship e
i
= cos + isin from which
(e
i

R
1
+ e
i

R
2
+ e
i

R
3
)(e
i

R
1
+ e
i

R
2
+ e
i

R
3
) =
= [(cos

k

R
1
+ isin

k

R
1
) + (cos

k

R
2
+ isin

k

R
2
) + (cos

k

R
3
+ isin

k

R
3
)]
[(cos

k

R
1
isin

k

R
1
) + (cos

k

R
2
isin

k

R
2
)(cos

k

R
3
isin

k

R
3
)]
= (cos

k

R
1
+ cos

k

R
2
+ cos

k

R
3
)
2
+ (sin

k

R
1
+ sin

k

R
2
+ sin

k

R
3
)
2
7
= [cos
2

R
1
+cos
2

R
2
+cos
2

R
3
+2(cos

R
1
cos

R
2
+cos

R
2
cos

R
3
cos

R
1
cos

R
3
)]
[sin
2

R
1
+sin
2

R
2
+sin
2

R
3
+2(sin

R
1
sin

R
2
+sin

R
2
sin

R
3
+sin

R
1
sin

R
3
)]
= 3 + 2cos

k (

R
1

R
2
) + 2cos

k (

R
2

R
3
) + 2cos

k (

R
1

R
3
)
= 3 + 2cosk
1
+ 2cosk
2
+ 2cos(k
1
k
2
)
where k
1
=

k a
1
, k
2
=

k a
2
.
The value of (e
i

R
1
+ e
i

R
2
+ e
i

R
3
) (e
i

R
1
+ e
i

R
2
+ e
i

R
3
) can thus
be represented as a function f(

k)
f(

k) = 3 + 2cosk
1
+ 2cosk
2
+ 2cos(k
1
k
2
) (21)
and the corresponding E
0
,E
1
,E
2
,E
3
values nally reads:
E
0
=
2p
(22)
E
1
= S
AB
H

AB
+ H
AB
S

AB
= 2s
0

0
(f(

k)) (23)
E
2
= H
2
AA
H
AB
H

AB
=
2
2p

2
0
(f(

k)) (24)
E
3
= S
2
AA
S
AB
S

AB
= 1 s
2
0
(f(

k)) (25)
(26)
Substituting the above values in E

k), we obtain:
E

k) =
(E
1
2E
0
) [(E
1
2E
0
)
2
4E
2
E
3
]
1/2
2E
3
=
(2s
0

0
f(

k) 2
2p
) [(2s
0

0
(f(

k)) 2
2p
)
2
4(
2
2p

2
0
(f(

k)))(1 s
2
0
(f(

k)))]
1/2
2(1 s
2
0
(f(

k)))
=
(2s
0

0
f(

k) + 2
2p
) [(4s
2
0

2
0
f
2
(

k) 8s
0

2p
f(

k) + 4
2
2p
(4 4s
2
0
f(

k))(
2
2p

2
0
f(

k))]
1/2
2(1 s
2
0
(f(

k)))
Expanding the terms inside the square root,
=
(2s
0

0
f(

k) + 2
2p
) [4s
2
0

2
0
f
2
(

k) 8s
0

2p
f(

k) + 4
2
2p
4
2
2p
+ 4
2
0
f(

k) + 4s
2
0

2
2p
f(

k) 4s
2
0

2
0
f
2
(

k)]
1/2
2(1 s
2
0
(f(

k)))
=
(2s
0

0
f(

k) + 2
2p
) [f(

k)(2
0
2s
0

2p
)
2
]
1/2
2(1 s
2
0
(f(

k)))
8
=
(2s
0

0
f(

k) + 2
2p
) (2
0
2s
0

2p
)
_
f(

k)
2(1 s
2
0
(f(

k)))
=
(s
0

0
f(

k) +
2p
) (
0
s
0

2p
)
_
f(

k)
(1 s
2
0
(f(

k)))
We obtain two values for E

k), namely
E

k) =
_

_
(s
0

0
f(

k)+
2p
)+(
0
s
0

2p
)

f(

k)
(1s
2
0
(f(

k)))
(s
0

0
f(

k)+
2p
)(
0
s
0

2p
)

f(

k)
(1s
2
0
(f(

k)))
E

k) =
_

2p
(1s
0

f(

k))+
0

f(

k)(1s
0

f(

k))
(1s
0

f(

k))(1s
0

f(

k))

2p
(1s
0

f(

k))
0

f(

k)(1s
0

f(

k))
(1s
0

f(

k))(1+s
0

f(

k))
E

k) =
_

_
(
2p
+
0

f(

k))(1s
0

f(

k))
(1s
0

f(

k))(1s
0

f(

k))
(
2p

f(

k))(1+s
0

f(

k))
(1s
0

f(

k))(1+s
0

f(

k))
The nal formula for E

k) is:
E

k) =

2p

0
_
f(

k)
1s
0
_
f(

k)
The values of
2p
,
0
, and s
0
are usually found by tting experimental or
rst principles data. The values that are taken are
2p
= 0 eV,
0
between
-2.5 and -3 eV, s
0
below 0.1.[1] Since s
0
is small, it is usually neglected. By
using
2p
= 0 eV,
0
= 2.78 and s
0
= 0.006 we obtain the band structure
shown in Fig. 4, where the E

k) values are plotted against

k along the high-

symmetry lines M--K-M. The values E > 0 correspond to the antibonding

states and the values E < 0 correspond to the bonding states.

9
-20
-10
0
10
20
E
n
e
r
g
y

(
e
V
)
VASP
TB - first nn
VASP and TB bands
TB bands-with first nearest neighbours
M K M
Figure 4: TB band structure of graphene-with nearest neighbours only
3.2 With second nearest neighbours:
For the A carbon atoms, the second nearest neighbours are A atoms present
at A
21
_
a

3
2
,
a
2
_
, A
22
_
a

3
2
,
a
2
_
, A
23
(0, a), A
24
_

3
2
,
a
2
_
, A
25
_

3
2
,
a
2
_
,
A
26
(0, a)
As per the denition,
H
AA
S
AA
= E
0
(27)
S
AB
H

AB
+ H
AB
S

AB
= E
1
(28)
H
2
AA
H
AB
H

AB
= E
2
(29)
S
2
AA
S
AB
S

AB
= E
3
(30)
Except H
AA
and S
AA
, all the other values remain the same ( second near-
est neighbours are A atoms).
General denition for H
AA
is,
H
AA
=
1
N

R
A

R
A

A
(r

R
A
|H|
A
(r

R
A
) (31)
10
R
A
= R
A
+ R
2i
Where i goes from 1 to 6.
H
AA
=
2p
+
1
u(k
x
, k
y
) Where,

1
=
1
N

A
(r

R
A
|H|
A
(r

R
A

S
AA
= 1 + s
1
u(k
x
, k
y
) Where,
s
1
=
1
N

A
(r

R
A
|
A
(r

R
A

Where u(k
x
, k
y
) = 2 cos(k
y
a) + 4 cos
_

3a
2
k
x
_
cos
_
a
2
k
y
_
E
0
= (
2p
+
1
u(k
x
, k
y
)) (1 + s
1
u(k
x
, k
y
)) (32)
E
1
= S
AB
H

AB
+ H
AB
S

AB
= 2s
0

0
(f(

k)) (33)
E
2
= H
2
AA
H
AB
H

AB
= (
2p
+
1
u(k
x
, k
y
))
2

2
0
(f(

k)) (34)
E
3
= S
2
AA
S
AB
S

AB
= (1 +
1
u(k
x
, k
y
))
2
s
2
0
(f(

k)) (35)
(36)
Where u(k
x
, k
y
) = 2 cos(k
y
a) + 4 cos
_

3a
2
k
x
_
cos
_
a
2
k
y
_
Substituting the above values, the energy eigen values are given by the
expression,
E

k) =
(E
1
2E
0
) [(E
1
2E
0
)
2
4E
2
E
3
]
1/2
2E
3
(37)
The parameters used for the TB bands are given in Table:1
11
-20
-10
0
10
20
E
n
e
r
g
y

(
e
V
)
VASP
TB-with second nn
VASP and TB bands
TB - with second nearest neighbours
M K M
Figure 5: TB band structure of graphene-with second nearest neighbours
3.3 With third nearest neighbours
For the A carbon atom, the third nearest neighbours are B atoms present at
B
31
_
a
2

3
,
a
2
_
, B
32
_
a
2

3
,
a
2
_
, B
31
_

3
, 0
_
So the elements H
AA
and S
AA
remain the same but the elements H
AB
and S
AB
include the additional terms due to the third nearest neighbouring
atoms.
E
0
= (
2p
+
1
u(k
x
, k
y
)) (1 + s
1
u(k
x
, k
y
))
E
1
= S
AB
H

AB
+ H
AB
S

AB
= 2s
0

0
(f(

k)) + (
2
s
0
+
0
s
2
)v(k
x
, k
y
) + 2s
2

2
(f(2

k))
E
2
= H
2
AA
H
AB
H

AB
= (
2p
+
1
u(k
x
, k
y
))
2

2
0
(f(

k)) + 2
0

2
v(k
x
, k
y
) +
2
2
(f(2

k))
_
E
3
= S
2
AA
S
AB
S

AB
= (1 +
1
u(k
x
, k
y
)
2

_
s
2
0
(f(

k)) + 2s
0
s
2
v(k
x
, k
y
) + s
2
2
(f(2

k))
_
Where v(k
x
, k
y
) = 4 cos (ak
y
) + 8 cos
_

3
2
ak
x
_
cos
_
a
2
k
y
_
+ 4 cos
_

3
2
ak
x
_
cos
_
3a
2
k
y
_
+ 2 cos (

3ak
x
)
Substituting the above values, the energy eigen values are given by the
expression,
12
E

k) =
(E
1
2E
0
) [(E
1
2E
0
)
2
4E
2
E
3
]
1/2
2E
3
-20
-10
0
10
20
E
n
e
r
g
y

(
e
V
)
VASP
TB -Third nn
VASP and TB bands
TB bands - With third nearest neighbours
M K M
Figure 6: TB band structure of graphene-with third nearest neighbours
Table 1: Parameters used for the TB model
Parameters 1
st
nn 2
nd
nn 3
rd
nn

2p
0 -0.28 eV -0.28

0
-2.78 eV -2.78 -2.78

1
-0.073 eV -0.073

2
-0.3 eV
s
0
0.06 0.06 0.06
s
1
0.002 0.002
s
1
0.001
It is to be noted that the parameters used for the rst, second and third
nearest neighbour bands are not varied i.e., the values are kept the same for
each case inorder to show the improvement of the tting with the inclusion of
the second and third nearest neighbour hoppings as compared to that of the
rst nearest neighbours. But for each case, the parameters could be chosen
freely inorder to obtain the best t.
13