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Dept of Phys

M.C. Chang

Energy bands
(<<) Nearly-free electron limit
Bragg reflection and energy gap
Bloch theorem
The central equation
Empty-lattice approximation

(>>) Tight-biding limit


For history on band theory, see , by , chap 4

Nearly-free electron (NFE) model


n NFE Model is good for Na, K, Al etc, in which the lattice potential
is only a small perturbation to the electron sea.
Free electron plane wave
rr
r
ik r
r
k (r ) = e , k x = nx 2 / L, ... etc
Consider 1-dim case, when we turn on a lattice potential with period
a, the electron wave will be Bragg reflected when k=
/a, which
forms two different types of standing wave. (Peierls, 1930)

c
= cce

h a2 cos(x / a),
h = i a2 sin(x / a).

+ = c eix / a + e ix / a =

Density distribution

ix / a

e ix / a

These 2 standing waves have different electrostatic energies.


The difference is the energy gap.
For U(x)=U cos(2x/a)

E g = dxU ( x )( e) | ( x )|2 | + ( x )|2


0

z
a

h
h

2e
= U dx cos(2x / a ) sin 2 x / a cos2 x / a = eU
a 0

Energy dispersion

Electrons group velocity is zero near the boundary


of the 1st Brillouin zone

Q: where are the energy gaps when U(x)=U1 cos(2x/a)+U2 cos(4x/a)?

The Kronig-Penny model (1930)

Let b0, but keeps bV0 a constant (called a Dirac comb), then

Calculated
electron energy
dispersion
Energy bands
(Kittel, p.170)

General theory for an electron in a weak periodic potential

|(x)|2 is the same in each unit cell.


Bloch theorem (1928)
The electron states in a periodic potential is of the form
rr
r
r
ik r
kr (r ) = e ukr (r )

where uk(r)= uk(r+R) is a cell-periodic function


The cell-periodic part uk(x) depends on the form of the
periodic potential.
A simple proof for 1-dim:

(x+a)=C(x)
Consider periodic BC,
(x+Na)=(x)=CN(x)
C=exp(i2s/N), s=0,1,2 N-1
Write (x) as uk(x) exp(i2sx/Na)
then uk(x) = uk(x+a)

Allowed values of k are determined by the B.C.


Periodic B.C. r (rr + N i ari ) = r (rr ), i = 1,2,3 ( N1 N 2 N 3 = N )
nk
nk
r
r
(3-dim case)
iN k a
e

= 1, i = 1,2,3
r r
N i k ai = 2mi , mi Z , i = 1,2,3
r m1 r m2 r m3 r
b1 +
b2 +
b3
k=
N1
N2
N3
i

This is similar to the discussion in chap 4 about the


allowed values of k for a phonon.
r
r
r
r
b
b
b
1 r r r
3
1
2
3
k =

= b1 (b2 b3 )
N1 N 2 N 3
N

F
GH

I
JK

1 ( 2 )
V
r r r
, a1 (a2 a3 ) = v =
N v
N
(2 ) 3
, as in the free - electron case.
=
V

r r r
b1 (b2 b3 )
r
=N
3
k

Therefore, there are N k-points in the 1st BZ, where N is


the total number of primitive cells in a crystal.

Difference between conductor/insulator (Wilson, 1931)


There are N k-points in an energy band, each k-point can be
occupied by two electrons (spin up and down).
each energy band has 2N seats for electrons.
If a solid has one valence electron per primitive cell, then the energy
band is half-filled (conductor)
If two electrons per primitive cell, then there are 2 possibilities
(a) no energy overlap or (b) energy overlap

insulator

conductor

For example, all alkali metals are conductors, while alkali earth
elements can be conductor/insulator. (Boron?)

How do we determine uk(x) from the potential U(x)? (1-dim case)


Keypoint: go to k-space to simplify the calculation
Fourier transform
1. the lattice potential

U ( x ) = U G eiGx

G=2pn/a

U ( x) = U G eiGx + e iGx = 2 U G cos Gx


G >0

2. the wave function


Schrodinger equation

(U0=0)

G >0

( x ) = C (k )eikx

k=2pn/L

p2

U
(
x
)
+

( x) = ( x)
2
m

Schrod. eq. in k-space


aka. the central eq.

h2 k 2
( k ) C (k ) + U GC (k G ) = 0, k
2m
G

Solve one k at a time, but notice each C(k) is related to


other C(k-G) (G)
For a given k, there are many eigen-energies n, with
corresponding eigen-vectors Cn.

Focus on one k in the first BZ


(and a specific n)
nk ( x) = Cn (k G )ei ( k G ) x
G

The Bloch state ynk(x) is a superposition of exp[i(k-g)x], exp[ikx], exp[i(k+g)x]


The energy of ynk(x) is n(k)

-g

(g=2p/a)
e

exp[i(k+g)x] exp[ikx]

exp[i(k-g)x]

If k is close to 0, then the most significant component of


y1k(x) is exp[ikx] (little superposition from other plane waves)
If k is close to g/2, then the most significant components of
y1k(x) and y2k(x) are exp[i(k-g)x] and exp[ikx], others can be
neglected.

For example, U(x) = 2U cos2px/a = U exp(2pix/a)+U exp(-2pix/a)


There are only 2 components Ug=U-g=U (g=2p/a)
Matrix form of the central eq.
O

F
GG
GG
GG
H

( k = h 2 k 2 / 2m)

kg

0
0

0
0

U
0

k+g
U

k 2 g

I F C ( k 2 g )I
JJ G C(k g) J cutoff for
0
GJ G C(k ) JJ = 0 kg/2!
0
JJ G C(k + g) J
U
G
J
J
K H C ( k + 2 g )K
0

k +2 g

The eigenvalues n(k) determines the energy band


The eigenvectors {Cn(k-G), "G} determines the
actual form of the Bloch states
nk ( x ) = Cn ( k G ) ei ( k G ) x = eikx unk ( x )
G

where unk ( x ) = Cn ( k G ) e iGx

check

r
r
n ,kr +Gr (r ) = n ,kr (r );
r r
r
r
r
ik R
n ,kr (r + R) = e n ,kr (r )

What are the eigen-energies and eigen-states when U=0?

Energy levels near zone boundary k=g/2


2 2
Cut-off form of the central eq. (k = h k / 2m, U < 0)

FG
H

kg

Energy eigenvalues
~
define k = k g / 2
then

IJ FG C(k g)IJ = 0
K H C( k ) K

U
k

(k ) =

FG
H

1
1
k g + k
2
2

~
2 g / 2
h2 k 2
~
(k ) = g /2 U +
1
2m
U

IJ
K

kg

i + b2U g
2

k ( x ) = C ( k g ) ei ( k g ) x + C ( k )eikx

Kittel, p.225

Sometimes it is convenient to
extend the domain of k with the
following requirement
nkr + Gr = nkr ,
r
r
n ,kr + Gr (r ) = n ,kr (r ).

NFE model in more than 1 dim (a rough discussion)


Band structure n(kx,ky) in 2-dim
Origin of energy gaps: Bragg reflection

Laue condition

r
G
$
k G =
2

G/2

Bragg reflection whenever k hits the BZ boundary

Kittel, p.227

Folding in 2-dim, the empty lattice approximation


l How to fold a parabolic surface back to the first BZ?
l Take 2D square lattice as an example
k-space

2p/a

Folded parabola along X (reduced zone scheme)


l In reality, there are
energy gaps at BZ
boundaries because of
the Bragg reflection
The folded parabola
along M is different

l Usually we only plot


the major directions, for
2D square lattice, they
are X, XM, M

2p/a

Folding in 3-dim

The energy bands for


an empty fcc lattice

Actual Band structure for


copper (fcc crystal, 3d104s1)

Tight binding model (details in chap 9)

Covalent solid,

Alkali metal,

d-electrons in
transition metals

noble metal