Electrons in a crystalline solid

Classical free electron gas (Drude Model)

electrons are completely free and independent and
follow a Maxwell statistic -completely classical approach.
Semi-Classical free electron gas (Sommerfeld model)
electrons are free and independent and follow the Fermi-
Dirac statistic (dense electron gas) -semi-classical
approach.
Nearly-free electron gas
Tight Bonding model
Density Functional theory
They are different ways to
'solve' the Schrdinger for a
many body system (the number
of electron is huge) The Bloch
theorem provide a way to write
the electron wavefunction.

From last week
Drude Model and Sommerfeld Model
+
+
+ +
+
The electrons are:
INDEPENDENT and FREE

Independent means that the e- don't interact with each other (it is
still a good approximation)

Free means that the e- act as free-particles: it is not a good

approximation since the electron sea feels the interaction with the
ions.
The free electron wave-functions are plane
waves of the form
k
(r) = e
i kr
, which are
running waves of momentum p = k

Failure of free-electron models
The free electron models can quite accurately describe heat
capacity, thermal conductivity, electrical conductivity,
magnetic susceptibility and electrodynamics of metals
The free electron model fails in explaining the differences
between metals, semi-conductors and insulators.
The free electron model fail in explaining the sign of the
charge carrier (the positive/negative value in R
H
)

Energy band in solids
Fermi energy lies
within a band of
accessible states
Fermi energy lies in the
gap, gap is relatively
small in size (~1 eV) so
that some e
-
s can be
excited
Fermi energy lies in the
gap, gap is relatively
large in size (~10 eV
electrons cannot be
excited to higher states)
insulators
metals
semiconductors
Fermi
Energy
Gap

Schrdingers Equation:
H Hamiltonian = Energy operator = Kinetic + Potential energy
expressions + external fields (electric, magnetic)

n
: Electronic wavefunctions (complex);
(r) =

{n}
dV: Charge density (real)
E
n
: Electronic energies
Temperature: How electronic states are occupied:
Maxwell-Boltzmann Distribution: f(E) = exp[-(E-E
F
)/k
B
T]
Fermi-Dirac Distribution: f(E) = 1/[1+exp(-(E-E
F
)/k
B
T)]

n
(r)=E
n

n
(r)
Electrons in a solid

Electrons in a solid
Schrdingers Equation:
A solid is a molecule with an infinite number (ca. 10
23
) of atoms.
Extended Solids: how to make the problem tractable?
(a) Amorphous (glasses): silicates, phosphates molecular fragments,
(b) Quasiperiodic: fragments based on building units,
(c) Crystalline: unit cells (translational symmetry) elegant
simplification!

n
(r)=E
n

n
(r)

Electrons in solid
U
x
U( x) =U
0
+U
1
cos
(
2 n
a
x
)
U
0
U
1
0

n
( x) =E
n

n
( x)
=
(

2
2m
d
2
dx
2
+U( x)
)

Wavefunction in a periodic potential
U(x) =U
0
+U
1
cos
(
2n
a
x
)
U
0
U
1
0
0
1
= U
Wavefunctions are plane waves and energy bands
are parabolic:
) ( t kx i
Ae

=
m
k
E
2
2 2

=
a
k
U

< <
0
1 Electrons wavelengths much larger than a, so wavefunctions
and energy bands are nearly the same as above
a
k
U

0
1 Electrons wavelengths approach a, so waves begin to be
strongly back-scattered :
) ( ) ( t kx i t kx i
Be Ae

= A B <
a
k
U

=
0
1
Electrons waves are strongly back-scattered (Bragg scattering)
so standing waves are formed:
[ ] [ ]
t i ikx ikx t kx i t kx i
e e e A e e C

= =
2
1
) ( ) (
There are two standing
waves!!!
j
+
=

+
= 2A
2
cos
2
(
nx
a
)
j

=2A
2
sin
2
(
nx
a
)

The Bloch Theorem: the idea
My calculations were only completed in the
summer when I wrote my thesis on 'The Quantum
Mechanics of Electrons in Crystal Lattice'
[Felix Bloch, , 1976]
Such a distance was
much too short to
explain the observed
resistances... To make
my life easy, I began by
considering
wavefunctions in a one-
dimensional periodic
potential. By straight
Fourier analysis I found
to my delight that the
wave differed from the
plane wave of free
electrons only by a
periodic modulation.
That's it!
How the electrons could sneak by all the ions in a metal so as to avoid a
mean free path of the order of atomic distances.

The Bloch Theorem
Let a be any vector in a lattice. Let be
n
a single electron solution to
the Schroedinger equation
Then there exists a wavevector k in the reciprocal lattice and a periodic
function u
k
(r) such that u
k
(r+R)=u
k
(r) such that
n,k
is of the form:

n
(r) =E
n

n
(r)
(

2
2m

2
+U(r)
)

n
(r) =E
n

n
(r)
where U(r+R) =U(r) R=n
1
a+n
2
b+n
3
c

n, k
(r) =e
i k
n
r
u
n, k
(r) r
u
n, k
(r+R) =u
n, k
(r)

n, k
(r+R) =
n, k
(r) R
This means that the Bloch function

n,k
(r) is a plane wave modulated
by the periodic function u
n,k
(r), with
the same periodicity of the lattice.

Periodic potential in 1D
Consider a one-dimensional lattice. The potential energies
of adjacent atoms overlap and form a periodic potential
field: U(x+na)=U(x). We will employ the periodicity to
calculate the energy levels of electrons (or solving the
Schrdinger equation).
L=Na

Bloch Theorem: the proof in 1D

n, k
(x+a) =
n,k
(x) e
ika

n, k
( x+Na) =
n, k
( x)
Thus,
n, k
( x+a) =C
n, k
( x)
L
N
1
2
N-1

Let a be any element of the lattice and let G be any element of the
reciprocal lattice. This means that Ga is an integer multiple of 2,
in other words:

First notice that the Bloch theorem implies:

Consider N identical lattice points
around a circular ring, each separated
by a distance a. Our task is to prove:
e
iGa
=1

n, k
(r+R) =
(
u
n, k
(r)e
i kr
)
e
i kR
=
n, k
(r)e
i kR

Bloch Theorem: the proof in 1D
(x+a) =C( x)
(x+Na) =C(x+(N1) a) =... =C
N
( x) =( x)
C
N
=1 =e
i2nn/N
where n=0,!1,!2,. ..
L
N
1
2
N-1
Taking into account
n, k
( x+a) =
n, k
( x)e
ika
=C
n, k
( x)
Imposing C =e
i2nn/N
=e
ika
Thus, k
n
=
2nn
Na
Bloch wave-
vector

n,k
(x+a) =C
n, k
( x) =
n, k
( x)e
ik
n
a

L
N
1
2
N-1
Born-von Karman PBC
The Born-von Karman boundary condition deals with the end points
of a crystal. Ordinarily, we would think that the two end points are
different from the internal points. For many applications, however,
distinguishing the boundary points from the internal points is not
necessary, because a crystal usually has a tremendous number of
lattice points (this is not true for quantum wells, quantum wires, and
quantum dots). The Born-von Karman boundary condition requires
that the wave functions at the two end points be equal to each other.
L=Na
a
N+1
a

Bloch wave function

Not all wavefunctions satisfy the Bloch Theorem. For example, if the
wavefunction is for a lattice with boundaries then it is not of the Bloch
form.

The wavefunction of two or more interacting electrons is not of the

Bloch form.
Bloch wavefunction for a
Silicon solid. Obtained
through the quantum-espresso
code and visualised by
Xcrysden-package

Band Structure
E
g
=

U( x)
|
j
+
j

dx
Where,
j
+
=

+
=2A
2
cos
2
(
nx
a
)
j

=2A
2
sin
2
(
nx
a
)

Periodicity and band structure
Free electrons
Extended zone
Reduced zone

Energy band in solids

n
=

2
2m
d
2

n
( x)
dx
2
= E
n

n
(x) = Asin
nn
L
x
c
F
=

2
2m
(
nN
2L
)
2
=

2
2m
k
F
2

n
=(

2
2m
+U( x))
d
2

n
( x)
dx
2

n, k
(x) = u
n, k
(x)e
ikx
with, k
n
=
2nn
Na
The opening of the gap is due to the
periodicity of the potential
E
F

Energy Bands in metals
What happens for a real metal?
the case of Cu, the Fermi surface is
a slightly perturbed sphere.

Comments on BT (I)

For a given wavevector and potential, there

are a number of solutions, indexed by n, to
Schrdinger's equation for a Bloch electron.
The index n appears in Blochs theorem
since there is a whole spectrum of eigenstates
that solve the Schrdinger's equation.
The solutions proposed by Bloch, called
bands, are separated in energy by a finite
spacing at each k.
The wave vector k can always be reduced to
a small value residing in the first Brillouin
zone, since k can be written as a base vector
k plus a reciprocal lattice vector G.
The eigenvectors and eigenvalues can be
written as periodic functions of wave vector:
E
n,(k+G)
= E
n,k
All the properties of electrons in a
periodic potential can be calculated from
this band structure and the associated
wavefunctions, at least within the
independent electron approximation.
E
k
x
a

E
-
E
+
E
g

The Bloch wavevector k multiplied by the reduced Planck's
constant, is the particle's crystal momentum p=k, with k inside the
first Brillouin zone. The momentum of the electron moving in a
periodic potential is no longer constant; for the standing waves
resulting from (multiple) reflections at the Brillouin zones it is
actually zero (because the velocity is zero), while k is not.
Comments on BT (II)
Using Blochs theorem, the propagation speed of an electron wave-
packet in a periodic crystal can be calculated from a knowledge of the
energy band along that direction in reciprocal space:
This means that an electron (with a specified wavevector) moves
through a perfect periodic lattice with a constant velocity; i.e., it moves
without being scattered or in any way having its velocity affected!
v
g
=
do
dk
=
1

dE
dk
(1D) v
g
=
1

k
E(k) (3D)

BT and central equation
Derivation of the central equation
Because of the periodicity of the potential, we can represent
it in terms of the reciprocal lattice vectors G:
We now expand the wavefunctions in terms of their Fourier
series components:
Substituting the results for U(x) and for (x) in the
Schrdinger equation, we get the following set of algebraic
equations:
U(x) = 2
G
U
G
e
iGx
( x) = 2
k
C(k) e
ikx
(

2
k
2
2m
E
)
C(k)2
G
C(kG)U
G
=0
central equation

Kronig-Penning Model (I)
Blochs theorem, along with the use of periodic boundary conditions,
allows us to calculate (in principle) the energy bands of electrons in a
crystal if we know the potential energy function experienced by the
electron. This was first done for a simple finite square well potential
model by Krnig and Penney in 1931:
(

2
2m
d
2
dx
2
+U( x))( x) =E( x)

k
( x+(a+b)) =e
ik(a+b)

k
( x)

1
( x) = Ae
i x
+Be
i x

2
( x) =Ce
ox
+D
ox
U
x
a
a+b
2a+b 2(a+b)
U
0
-b
1 1 1 1 1 2 2 2 2 2 2

Kronig-Penning Model (II)

1
( x) = Ae
i x
+Be
i x

2
(x) =Ce
ox
+D
ox
A+B =C+D
i ( A+B) =o(C+D) x =0
Ae
i a
+Be
i a
=Ce
oa
+D
oa
i (Ae
i a
+Be
i a
) =o(Ce
oa
+D
oa
) x=a
U
x
a
a+b
2a+b 2(a+b)
U
0
-b
1 1 1 1 1 2 2 2 2 2 2

2
(a) =
2
(a(a+b))e
ik(a+b)
=
2
(b)e
ik( a+b)
where kBloch' s wavevector

2
(a) = Ae
i a
+Be
i a

Kronig-Penning Model (III)
1 1 1 1
i i o o
e
i a
e
i a
e
ob
e
ik(a+b)
e
ob
e
ik(a+b)
i e
i a
i e
i a
oe
ob
e
ik(a+b)
oe
ob
e
ik( a+b)
A
B
C
D
= 0
(

2
o
2
2o
)
sin(a) sinh(ob)+cos(a)cosh(ob) =cos|k(a+b)
o =
.
2m(U
0
E)

2
=
.
2mE

2

Kronig-Penning Model (IV)
(

2
o
2
2o
)
sin(a) sinh(ob)+cos(a)cosh(ob) =cos|k(a+b) if EU
0
(
o
2

2
2o
)
sin(a) sin(ob)+cos(a)cos(ob) =cos|k(a+b) if E>U
0
o =
.
2m(U
0
E)

2
=
.
2mE

2
Limit case ,let be ob-0 as U
0
-
So, sin(ob)(ob) ; cosob =1
P
(a+b)
sin(a+b)+cos(a+b) =cos|k(a+b)
where P =lim
b-0; U
0
-
(
o
2
ab
2
)

Kronig-Penning Model (V)
P
(a+b)
sin(a+b)+cos(a+b) =cos|k(a+b)
where P =(
o
2
ab
2
) =
mEab

2
; =
.
2mE

2
Dispersion relation
establishes a relation
between energy E
and quasi-
momentum k.
There are certain
energy intervals
for which no real k
can satisfy the
dispersion relation.
No states can have
these energies.
These regions are
called forbidden
bands.