Section 1.

2-3
Homework from this section: 1.5
(We will do a similar problem in class today)

Blochs Theorem and
Krnig-Penney Model



For review/introduction of Schrodinger equation:
http://web.monroecc.edu/manila/webfiles/spiral/6schrodingereqn.pdf
Learning Objectives for Today
After todays class you should be able to:
Apply Blochs theorem to the Kronig-
Penney model or any other periodic
potential
Explain the meaning and origin of
forbidden band gaps
Begin to understand the Brillouin zone
For another source on todays topics, see
Ch. 7 of Kittels Intro to Solid State Physics.
Crystal basics to prepare us for next class


Realistic Potential in Solids
Multi-electron atomic potentials are complex
Even for hydrogen atom with a simple
Coulomb potential solutions are quite
complex
So we use a model infinite one-dimensional
periodic potential to get insight into the
problem (last time, looked at 1-6 atoms)
Periodic Potential
For one dimensional case where atoms (ions) are
separated by distance a, we can write condition of
periodicity as
) ( ) ( n a x V x V + =
a
Section 1.3: Blochs Theorem
This theorem gives the electron wavefunction in the
presence of a periodic potential energy.
We will prove 1-D version, AKA Floquets theorem.
(3D proof in the book)
When using this theorem, we still use
the time-indep. Schrodinger equation
for an electron in a periodic potential
E r V
m
=
(

+ V ) (
2
2
2

) ( ) ( r V T r V

= +
where the potential energy
is invariant under a lattice
translation of a
In 3D (vector):
c w b v a u T

+ + =
) ( ) ( n a x V x V + =
Bloch Wavefunctions
Blochs Theorem states that for a particle moving
in the periodic potential, the wavefunctions (x)
are of the form




u
k
(x) has the periodicity of the atomic potential
The exact form of u(x) depends on the potential
associated with atoms (ions) that form the solid
) ( ) (
) ( , ) ( ) (
a x u x u
x u where e x u x
k k
k
ikx
k
+ =
=

function periodic a is
a
Main points in the proof of
Blochs Theorem in 1-D
1. First notice that Blochs theorem implies:
Can show that this formally implies
Blochs theorem, so if we can prove it
we will have proven Blochs theorem.
T k i r k i
k k
e e T r u T r

+ = + ) ( ) (
T k i r k i
k
e e r u

= ) (
T k i
k
e r

= ) (
Or
just:
T k i
k k
e r T r

= + ) ( ) (
2. To prove the statement shown above in 1-D:
Consider N identical lattice points around a
circular ring, each separated by a distance a.
Our task is to prove: ika
e x a x ) ( ) ( = +
1
2 N
3
) ( ) ( x Na x = +
Built into the ring
model is the periodic
boundary condition:
) ( ) (
, ) ( ) (
a x u x u
e x u x
k k
ikx
k
+ =
=
Proof of Blochs Theorem in 1-D: Conclusion
If we apply this translation N times we
will return to the initial atom position:
Now that we know C we can rewrite
) ( ) ( ) ( x x C Na x
N
= = +
This
requires
1 =
N
C
And has the
most general
solution:
,... 2 , 1 , 0
2
= = n e C
ni N t
ika N ni
e e C = =
/ 2t
Or:
Where we define the
Bloch wavevector:
Na
n
k
t 2
=
. . . ) ( ) ( ) ( D E Q x e x C a x
ika
= = +
The symmetry of the ring (and last lecture) implies
that we can find a solution to the wave equation:
) ( ) ( x C a x = +
1
2 N
3
Consequence of Blochs Theorem
Probability of finding the electron


Each electron in a crystalline solid belongs
to each and every atom forming the solid




Very accurate for metals where electrons are
free to move around the crystal!
Makes sense to talk about a specific x ( n a)
) ( ) ( a x P x P + =
Using Blochs Theorem: The Krnig-Penney Model
Blochs theorem allows us to calculate the energy bands of electrons
in a crystal if we know the potential energy function.
First done for a chain of finite square well potentials model by Krnig
and Penney in 1931 with E<V
0
Each atom is represented by
a finite square well of width
a and depth V
0
. The atomic
spacing is a+b.
We can solve the SE in each region of space:

E x V
dx
d
m
=
(

+ ) (
2
2
2 2

0 < x < a
iKx iKx
I
Be Ae x

+ = ) (
m
K
E
2
2 2

=
-b < x < 0
V
x
0 a
a+b
2a+b 2(a+b)
V
0
-b
x x
II
De Ce x
k k

+ = ) (
m
E V
2
2 2
0
k
=
I wish the book had selected
different letters than K and
k, but staying consistent
Boundary Conditions and Blochs Theorem
x = 0
The solutions of the SE require that the
wavefunction and its derivative be
continuous across the potential boundaries.
Thus, at the two boundaries (which are
infinitely repeated):
iKx iKx
I
Be Ae x

+ = ) (
x x
II
De Ce x
k k

+ = ) (
Now using Blochs theorem for a
periodic potential with period a+b:
x = a
) (a Be Ae
II
iKa iKa
= +

D C B A + = +
(1) ) ( ) ( D C B A iK = k
(2)
) (
) ( ) (
b a ik
II II
e b a
+
=
k = Bloch
wavevector
Now we can write the boundary conditions at x = a:
) (
) (
b a ik b b iKa iKa
e De Ce Be Ae
+
+ = +
k k
(3)
) (
) ) ( ) ( ( ) ( ) (
b a ik b b iKa iKa
e De ik Ce ik Be ik iK Ae ik iK
+
+ = +
k k
k k
(4, deriv.)
The four simultaneous equations
(1-4) can be written compactly in
matrix form
ikx
k
e x u x

= ) ( ) (
Results of the Krnig-Penney Model
Since the values of a and b are inputs to the model, and k
depends on V
0
and the energy E, we can solve this system of
equations to find the energy E at any specified value of the
Bloch wavevector k. What is the easiest way to do this?
0
) ( ) ( ) ( ) (
1 1 1 1
) ( ) (
) ( ) (
=
(
(
(
(

(
(
(
(

+ + +



+ +
+ +
D
C
B
A
e e ik e e ik e ik iK e ik iK
e e e e e e
iK iK
b a ik b b a ik b iKa iKa
b a ik b b a ik b iKa iKa
k k
k k
k k
k k
Taking the determinant, setting it equal to zero and lots of algebra gives:
( ) ( ) ( ) ( ) | | ) ( cos cosh cos sinh sin
2
2 2
b a k b Ka b Ka
K
K
+ = +
|
|
.
|

\
|
k k
k
k
By reducing the barrier width b (small b), this can be simplified to:
Graphical
Approach
Right hand side cannot exceed 1, so values exceeding will
mean that there is no wavelike solutions of the Schrodinger eq.
(forbidden band gap)
( ) ( ) ) cos( cos sin
2
2
ka Ka Ka
K
b
= +
|
|
.
|

\
| k
Ka
Plotting left side of equation
Gap occurs
at Ka=Nt or
K=Nt/a
( ) ( ) ( ) ( ) | | ) ( cos cosh cos sinh sin
2
2 2
b a k b Ka b Ka
K
K
+ = +
|
|
.
|

\
|
k k
k
k
small b
m
K
E
2
2 2

=
Not really much different
Single Atom
Multiple Atoms
Greek Theater Analogy: Energy Gaps
What Else Can We
Learn From This
Model?
Exercise 1.4
( ) ( ) ) cos( cos sin
2
2
ka Ka Ka
K
b
= +
|
|
.
|

\
| k

Different Ways to Plot It
Extended Zone Scheme
Note that the larger the energy, the larger the band/gap is (until
some limit).
Ka
The range -t<ka<t is called
the first Brillouin zone.
Atoms
Different x axis
k = Bloch
wavevector
y=cos ka
( ) ( ) ) cos( cos sin
2
2
ka Ka Ka
K
b
= +
|
|
.
|

\
| k
Different Representations of E(k)
Reduced zone scheme
All states with |k| > t/a are
translated back into 1
st
BZ
Frequently only one side is
shown as they are
degenerate.
In 3D, often show one side
along with dispersion
along two other directions
(e.g. 100, 110, 111)
Band diagrams can refer to either E vs.
real space or E vs momentum space k
Real space examples
Momentum space example
21
Compare to the free-electron model
Free electron dispersion
E
k

Lets slowly turn on the periodic potential
...with first Brillouin zone:
t/a t/a
(a the lattice constant)
t/a t/a
2
2 2 2
( )
2
x y z
E k k k
m
= + +

Lets draw it in 3D!
Electron Wavefunctions in a
Periodic Potential
(Another way to understand the energy gap)
Consider the following cases:
Electrons wavelengths much larger than atomic spacing
a, so wavefunctions and energy bands are nearly the
same as above
0
1
= V
) ( t kx i
Ae
e

=
m
k
E
2
2 2

=
a
k
V
t
<<
= 0
1
Wavefunctions are plane
waves and energy bands
are parabolic:
E
k t/a t/a
V
x
0 a
a+b
2a+b 2(a+b)
V
1
-b
How do X-rays Work?
The soft tissue in your
body is composed of
smaller atoms, and so
does not absorb X-ray
photons particularly
well. The calcium
atoms that make up
your bones are much
larger, so they are
better at absorbing
X-ray photons.
Consequence of Blochs Theorem
Similar to how radio waves pass through us without affecting
Electron Wavefunctions in a
Periodic Potential
U=barrier potential
Consider the following cases:
Electrons wavelengths much larger than a, so
wavefunctions and energy bands are nearly the same
as above
0
1
= V
) ( t kx i
Ae
e

=
m
k
E
2
2 2

=
a
k
V
t
<<
= 0
1
Wavefunctions are plane
waves and energy bands
are parabolic:
a
k
V
t
=
= 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
e e e

= =
2
1
) ( ) (
a
k
V
t
s
= 0
1 Electrons wavelengths approach a, so waves begin to
be strongly back-scattered by the potential:
) ( ) ( t kx i t kx i
Be Ae
e e

= A B<
E
k t/a t/a
The nearly-free-electron model
(Standing Waves)
Either:
Nodes at ions
Or:
Nodes midway
between ions
a
Due to the , there are two such standing waves possible:
| |
t i t i ikx ikx
e kx A e e e A
e e

+
= + = ) cos( 2
2
1
2
1
| |
t i t i ikx ikx
e kx iA e e e A
e e

= = ) sin( 2
2
1
2
1
These two approximate solutions to the S. E. at have
very different potential energies. has its peaks at x = a,
2a, 3a, at the positions of the atoms, where V is at its
minimum (low energy wavefunction). The other solution,
has its peaks at x = a/2, 3a/2, 5a/2, at positions in between
atoms, where V is at its maximum (high energy wavefunction).
a
k
t
=
+

| |
t i ikx ikx
e e e A
e

=
2
1
The nearly-free-electron model
Strictly speaking we should have looked at the probabilities
before coming to this conclusion:
a

~
2

2
| |
t i t i ikx ikx
e kx A e e e A
e e

+
= + = ) cos( 2
2
1
2
1
| |
t i t i ikx ikx
e kx iA e e e A
e e

= = ) sin( 2
2
1
2
1
) ( cos 2
2 2 *
a
x
A
t
=
+ +
) ( sin 2
2 2 *
a
x
A
t
=

Different energies for electron standing waves
28
E
k
Summary: The nearly-free-electron model
BAND GAPS APPEAR AT EACH BRILLOUIN ZONE EDGE
-2/a /a /a 2/a
In between the two energies
there are no allowed energies;
i.e., wavelike solutions of the
Schrodinger equation do not
exist.

Forbidden energy bands form
called band gaps.
The periodic potential
V(x) splits the free-
electron E(k) into energy
bands separated by gaps
at each BZ boundary.
E
-
E
+
E
g
E
k
Approximating the Band Gap
BAND GAPS APPEAR AT EACH BRILLOUIN ZONE EDGE
-2/a /a /a 2/a
}
=
+
~
a
x
a
x
a
dx x V E E
0
2 2
) ( cos ) (
t
E
-
E
+
E
g
}
=
+
+
= =
a
x
g
dx x V E E E
0
2 2
] )[ (
For square potential: V(x) =V
o
for specific values of x (changes integration limits)


) ( cos 2
2 2 *
a
x
A
t
=
+ +
) ( sin 2
2 2 *
a
x
A
t
=

Crystal Directions
Figure shows
[111] direction

Choose one lattice point on the line as an
origin (point O). Choice of origin is
completely arbitrary, since every
lattice point is identical.
Then choose the lattice vector joining O to
any point on the line, say point T. This
vector can be written as;

R = n
1
a + n
2
b + n
3
c

To distinguish a lattice direction from a
lattice point, the triplet is enclosed in
square brackets [ ...]. Example: [n
1
n
2
n
3
]
[n
1
n
2
n
3
] is the smallest integer of the
same relative ratios. Example: [222]
would not be used instead of [111].
Negative directions can be written as

] [
3 2 1
n n n
Also sometimes
[-1-1-1]