Introduction

to the
Tightbinding
(LCAO)
Method


Tightbinding: 1 Dimensional Model #1

Consider an Infinite Linear Chain of identical atoms, with 1
s-orbital valence e
-
per atom & interatomic spacing = a
Approximation: Only Nearest-Neighbor interactions.
(Interactions between atoms further apart than a are ~ 0).
This model is called the Monatomic Chain.
Each atom has s electron orbitals only!
Near-neighbor interaction only means that thes orbital on site
n interacts with the s orbitals on sites n 1 & n + 1 only!

n = Atomic Label a
| |
n = -3 -2 -1 0 1 2 3 4
The periodic potential V(x) for this Monatomic Linear
Chain of atoms looks qualitatively like this:
n = -4 -3 -2 -1 0 1 2 3
a
| |
V(x) = V(x + a)
The localized atomic orbitals on each site for this Monatomic
Linear Chain of atoms look qualitatively like this:
n = -4 -3 -2 -1 0 1 2 3
The spherically symmetric s orbitals on each site overlap
slightly with those of their neighbors, as shown. This
allows the electron on site n to interact with its
nearest-neighbors on sites n 1 & n + 1!

a
| |
The True Hamiltonian in the solid is:
H = (p)
2
/(2m
o
) + V(x), with V(x) = V(x + a).
I nstead, approximate it as H ~
n
H
at
(n) +
n,n'
U(n,n')
where, H
at
(n) Atomic Hamiltonian for atom n.
U(n,n') Interaction Energy between atoms n & n'.
Use the assumption of only nearest-neighbor interactions:
U(n,n') = 0 unless n' = n -1 or n' = n +1

With this assumption, the Approximate Hamiltonian is
H ~
n
[H
at
(n) + U(n,n -1) + U(n,n + 1)]

H ~
n
[H
at
(n) + U(n,n -1) + U(n,n + 1)]
Goal: Calculate the bandstructure E
k
by solving the
Schrdinger Equation:
H
k
(x) = E
k

k
(x)
Use the LCAO (Tightbinding) Assumptions:
1. H is as above.
2. Solutions to the atomic Schrdinger Equation are known:
H
at
(n)
n
(x) = E
n

n
(x)
3. In our simple case of 1 s-orbital/atom:
E
n
= = the energy of the atomic e
-
(known)
4.
n
(x) is very localized around atom n
5. The Crucial (LCAO) assumption is:

k
(x)
n
e
ikna

n
(x)
That is, the Bloch Functions are linear combinations of atomic orbitals!
Dirac notation: E
k
<
k
|H|
k
>
(This Matrix Element is shorthand for a spatial integral!)

Using the assumptions for H &
k
(x) already listed:
E
k
= <
k
|
n
H
at
(n) |
k
> + <
k
|[
n
U(n,n-1) + U(n,n-1)]|
k
>
also note that H
at
(n)|
n
>

= |
n
>


The LCAO assumption is: |
k
>


n
e
ikna
|
n
>

Assume orthogonality of the atomic orbitals:
<
n
|
n'
> =
n,n'
(= 1, n = n'; = 0, n = n')
Nearest-neighbor interaction assumption:
There is nearest-neighbor overlap energy only! ( = constant)
<
n''
|U(n,n 1)|
n'
> - ; (n'' = n, & n' = n 1)
<
n''
|U(n,n 1)|
n'
> = 0, otherwise
It can be shown that for > 0,
this must be negative!
As a student exercise, show that the energy band of this model is:
E
k
= - 2cos(ka) or E
k
= - 2 + 4 sin
2
[()ka]

A trig identity was used to get last form. & are usually taken as parameters
in the theory, instead of actually calculating them from the atomic
n
The Bandstructure for this monatomic chain with nearest-neighbor
interactions only looks like (assuming 2 < ): (E
T
E
k
- + 2)






Its interesting to note that:
The form E
k
= - 2cos(ka)
is similar to Krnig-Penney model
results in the linear approximation
for the messy transcendental
function! There, we got:
E
k
= A - Bcos(ka)
where A & B were constants.

E
T
4
n = -1 0 1

Tightbinding: 1 Dimensional Model #2
~ A 1-dimensional semiconductor!

Consider an Infinite Linear Chain consisting of 2 atom types, A
& B (a crystal with 2-atom unit cells), 1 s-orbital valence e
-
per atom &
unit cell repeat distance = a.
Approximation: Only Nearest-Neighbor interactions.
(Interactions between atoms further apart than ~ ( )a are ~ 0).
This model is called the Diatomic Chain.
A B A B A B A
| |

a
The True Hamiltonian in the solid is:
H = (p)
2
/(2m
o
) + V(x), with V(x) = V(x + a).
I nstead, approximate it (with = A or =B) as
H ~
n
H
at
(,n) +
n,'n'
U(,n;',n')
where, H
at
(,n) Atomic Hamiltonian for atom in cell n.
U(,n;',n') Interaction Energy between atom of type
in cell n & atom of type ' in cell n'.
Use the assumption of only nearest-neighbor interactions:
The only non-zero U(,n;',n')
are U(A,n;B,n-1) = U(B,n;A,n+1) U(n,n-1) U(n,n+1)
With this assumption, the Approximate Hamiltonian is:
H ~
n
H
at
(,n) +
n
[U(n,n -1) + U(n,n + 1)]

H ~
n
H
at
(,n) +
n
[U(n,n -1) + U(n,n + 1)]
Goal: Calculate the bandstructure E
k
by solving the Schrdinger Equation:
H
k
(x) = E
k

k
(x)
Use the LCAO (Tightbinding) Assumptions:
1. H is as above.
2. Solutions to the atomic Schrdinger Equation are known:
H
at
(,n)
n
(x) = E
n

n
(x)
3. In our simple case of 1 s-orbital/atom:
E
An
=
A
= the energy of the atomic e
-
on atom A
E
Bn
=
B
= the energy of the atomic e
-
on atom B
4.
n
(x) is very localized near cell n
5. The Crucial (LCAO) assumption is:

k
(x)
n
e
ikna

n
(x)
That is, the Bloch Functions are linear combinations
of atomic orbitals!
Note!!
The C

s are unknown

Dirac Notation: Schrdinger Equation: E
k
<
k
|H|
k
>
<
An
|H|
k
> = E
k
<
An
|H|
k
> (1)
Manipulation of (1), using LCAO assumptions, gives (student
exercise):

A
e
ikna
C
A
+ [e
ik(n-1)a
+ e
ik(n+1)a
]C
B
= E
k
e
ikna
C
A
(1a)
Similarly: <
Bn
|H|
k
> = E
k
<
Bn
|H|
k
> (2)
Manipulation of (2), using LCAO assumptions, gives (student exercise):

B
e
ikna
C
B
+ [e
ik(n-1)a
+ e
ik(n+1)a
]C
A
= E
k
e
ikna
C
A
(2a)

Here, <
An
|U(n,n-1)|
B,n-1
> <
Bn
|U(n,n+1)|
A,n+1
>
= constant (nearest-neighbor overlap energy) analogous
to in the previous 1d model
Student exercise to show that these simplify to:
0 = (
A
- E
k
)C
A
+ 2cos(ka)C
B
, (3)

and
0 = 2cos(ka)C
A
+ (
B
- E
k
)C
B
, (4)


A
,
B
, are usually taken as parameters in the theory, instead of
computing them from the atomic
n
(3) & (4) are linear, homogeneous algebraic equations for C
A
& C
B

22 determinant of coefficients = 0
This gives: (
A
- E
k
)(
B
- E
k
) - 4
2
[cos(ka)]
2
= 0
A quadratic equation for E
k
!
2 solutions: a valence band
& a conduction band!
Results:
Bandstructure of the Diatomic Linear Chain (2 bands):
E

(k) = ()(
A
+
B
) [()(
A
-
B
)
2
+ 4
2
{cos(ka)}
2
]
This gives a k = 0 bandgap of
E
G
= E
+
(0) - E
-
(0) = 2[()(
A
-
B
)
2
+ 4
2
]

For simplicity, plot in the case
4
2
<< ()(
A
-
B
)
2
&
B


>
A

Expand the [ .]

part of E

(k) & keep the lowest order term

E
+
(k) ~
B
+ A[cos(ka)]
2
, E
-
(k) ~
A
- A[cos(ka)]
2

E
G
(0) ~
A

B
+ 2A

, where A (4
2
)/|
A
-
B
|


Bandstructure of a 1-dimensional semiconductor:


Tightbinding Method: 3 Dimensional Model
Model: Consider a monatomic solid, 3d, with only
nearest-neighbor interactions. Hamiltonian:
H = (p)
2
/(2m
o
) + V(r)
V(r) = crystal potential,
with the full lattice symmetry & periodicity.
Assume (R,R' = lattice sites):
H ~
R
H
at
(R) +
R,R'
U(R,R')
H
at
(R) Atomic Hamiltonian for atom at R
U(R,R') Interaction Potential between atoms at R & R'
Near-neighbor interactions only!
U(R,R') = 0 unless R & R' are nearest-neighbors
Goal:
Calculate the bandstructure E
k
by solving the Schrdinger Equation:
H
k
(r) = E
k

k
(r)
Use the LCAO (Tightbinding) Assumptions:
1. H is as on previous page.
2. Solutions to the atomic Schrdinger Equation are known:
H
at
(R)
n
(R) = E
n

n
(R), n = Orbital Label (s, p, d,..),

E
n
= Atomic energy of the e
-
in orbital n
3.
n
(R) is very localized around R
4. The Crucial (LCAO) assumption is:

k
(r) =
R
e
ik-R

n
b
n

n
(r-R) (b
n
to be determined)

n
(R): The atomic functions are orthogonal for different n & R
That is, the Bloch Functions are linear combinations of
atomic orbitals!
Dirac Notation: Solve the Schrdinger Equation: E
k
<
k
|H|
k
>
The LCAO assumption:
|
k
> =
R
e
ik-R

n
b
n
|
n
> (1)
(b
n
to be determined)
Consider a particular orbital with label m:
<
m
|H|
k
> = E
k
<
m
|H|
k
> (2)
Use (1) in (2).
Then use
1. The orthogonality of the atomic orbitals
2. The assumed form of H
3. The fact that
n
(R) is very localized around R
4. That we know the atomic solutions to H
at
|
n
> = E
n
|
n
>
5. The nearest neighbor assumption that U(R,R') = 0
unless R & R' are nearest-neighors.
Manipulate (several pages of algebra) to get:
(E
k
- E
m
)b
m
+
n

R=0
e
ik-R

mn
(R)b
n
= 0 , (I)
where:
mn
(R) <
m
|U(0,R)|
n
> Overlap Energy I ntegral
The
mn
(R) are analogous to the & in the 1d models. They are
similar to V
ss
, etc. in real materials, discussed next! The integrals
are horrendous to do for real atomic
m
! In practice, they are
treated as parameters to fit to experimental data.
Equation (I): Is a system of N homogeneous, linear, algebraic
equations for the coefficients b
n
. N = number of atomic orbitals.
Equation (I) for N atomic states
The solution is obtained by taking an N N determinant!
This results in N bands which have their roots in the atomic orbitals!
If the
mn
(R) are small, each band can be thought of as
E
k
~ E
n
+ k dependent corrections
That is, the bands are ~ atomic levels + corrections

Equation (I): A system of homogeneous, linear, algebraic
equations for the b
n

N atomic states Solve an N N determinant!
N bands
Note: Weve implicitly assumed 1 atom/unit cell.
If there are n atoms/unit cell, we get nN equations & nN bands!
Artificial Special Case #1: One s level per atom
1 (s-like) band
Artificial Special Case #2: Three p levels per atom
3 (p-like) bands
Artificial Special Case #3:
One s and three p levels per atom & sp
3
bonding
4 bands
NOTE that
For n atoms /unit cell, multiply by n to get the number of bands!
Back to:
(E
k
- E
m
)b
m
+
n

R=0
e
ik-R

mn
(R)b
n
= 0 , (I)
where:
mn
(R) <
m
|U(0,R)|
n
>
Overlap Energy I ntegral
Also: Assume nearest neighbor interactions only

R=0
is ONLY over nearest neighbors!
Artificial Special Case #1: One s level per atom
1 (s-like) band: E
k
= E
s
-
R=nn
e
ik-R
(R)
But (R) = is the same for all neighbors so:
E
k
= E
s
-
R=nn
e
ik-R

Assume, for example, a simple cubic lattice:
E
k
= E
s
-2[cos(k
x
a) + cos(k
y
a) +cos(k
z
a)]

Artificial Special Case #2:
Three p levels per atom.
Gives a 3 3 determinant to solve.
3 (p-like) bands
Student exercise!!
Artificial Special Case #3:
One s and three p levels per atom & sp
3
bonding
Gives a 3 3 determinant to solve.
4 bands
Student exercise!!