Electrons in a weak periodic potential
Assumptions:
1. Static defect-free lattice perfectly periodic potential.
2. Weak potential perturbative effect on the free electron states.
Perfect periodicity of the lattice potential implies that any electronic property we deduce will
also be influenced by this periodicity.
Bloch states: Average potential at a point is U(r). Assume independent electron picture, the
single particle Schrodinger equation is:
Using Blochs Theorem;
with
periodic in the lattice i.e.
Note that
implying
on
is not periodic in the real lattice. But ant measurable property will depend
which is periodic in the real lattice.
is called the Bloch function. In terms f the Bloc function the Schrodinger equation
becomes,
or
----(1)
or
----- (2)
This equation is difficult to solve for any general potential U(r) the periodicity of the lattice
lets us see some general features of the solution even without solving.
A. Quantization of k: Because of the lattice periodicity it is enough to solve the equation
in one primitive cell of the reciprocal lattice thus independent k values will have to be
confined to the first Brillouin zone
- the values of k will be quantized
to
, being and integer.
B. How many values of k relevant: The total number of independent values of k =L/a=N,
the number of lattice sites.
C. Significance of k:
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implying that the Bloch state is not an eigen state of the momentum operator this is
expected as the translational invariance of the system is broken by the lattice
potential. k is called the crystal momentum it determines the transition rules in
scattering problems (we shall see this later in the course when we do phonons)- it also
determines the phase factor the wave function picks up as it moves by a lattice
translation vector
D. Formation of energy bands: Equation (1) is an eigenvalue problem in a box (the
primitive lattice) for a given value of k there will be an infinite number of discrete
values of the energy
with the corresponding eigenfunction
.
The values of energy for all k for a given n form an energy band.
Figure 1:The energy levels of electrons moving in the periodic potential of one dimensional chains made up of 5
and 40 atoms
Note that for a periodic lattice k and k+G denote the same physical states. To see this
consider outside the 1st Brillouin zone bring it in using
.
with
. Probability of finding an electron at r with wave-vector is
proportional to
which equals to the probability of finding an electron
there with wave-vector
. In this sense the two states
and are equivalent.
For example consider the energy eigenvalues for
and
. Energy in the state is
given by:
Substitute
which tells us that
eigenvalue.
and use
to get
all equivalent states are associated with the same energy
Nearly free electron approximation Empty lattice approximation: Take the Sommerfeld free
electron states treat the lattice as a weak perturbation - free electron states smoothly evolve
into the Bloch states as the potential is slowly turned on we shall see later that the free
electron states and the Bloch states in a weak periodic potential differ appreciably only at the
centre and at the ends of the Brillouin zones hence this approach is justified post priori.
Writing the potential and the Bloch function in terms of their Fourier components:
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and
Substitute it in equation (1), multiply form left by
primitive cell to get
In the limit
and integrate over the volume of the
; the solutions are either
or
for a particular value of
.
The solution in the empty lattice for the band of index n is therefore particularly simple: apart
from a single
, all reciprocal-lattice vectors have vanishing coefficients in the expansion.
The normalized Bloch function of this state is then
Thus there is a direct one-to-one correspondence between the band indices n and the
reciprocal lattice vectors .
Band structure of electron in a 1-D lattice
Lattice length , lattice spacing
; with
. The allowed values of
with
. In the empty lattice approximation:
This looks different form the free electron energy derived using Sommerfeld model,
The apparent difference becomes clear below.
Different zone schemes:
a. Reduced zone scheme: All the bands are drawn in the first Brillouin zone. (see
Figure 2).
b. Repeated/periodic zone scheme: Every band is drawn in every Brillouin zone (see
Figure 3).
c. Extended-zone scheme: Different bands are drawn in different Brillouin zones (see
Figure 4).
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Figure 2: Dispersion
relation of free
electrons in empty
lattice approx in
reduced zone
representation.
Figure 3: Dispersion relation of
free electrons in empty lattice
approx in repeated zone scheme
Figure 4: Dispersion relation of
free electrons in empty lattice
approx in extended zone scheme
The infinite number of solutions associated with a given k can also be distributed among the
infinite number of vectors
in such a way that one solution should belong to each
equivalent vector. The reciprocal lattice can be broken up into Brillouin zones of different
orders using the same procedure for creating Wigner-Seitz cell. The assignment of the states
to the zones is then done simply by assigning the states of the first band to the wave vectors
in the first Brillouin zone, the states of the second band to the wave vectors in the second
Brillouin zone, and so forth. This is how the extended-zone scheme is obtained.
Conversely energy eigenvalues of the electrons moving through the empty lattice for a given
k values in the reduced zone scheme can be got from the free-electron dispersion curve by
finding the equivalent k values inside the first Brillouin zone for each wave number outside
of it, and then shifting the energy eigenvalue to this k value. This procedure is called zone
folding.
Fermi surface in empty lattice approximation: Fermi-Dirac statistics determine the filling of
the energy levels Fermi surface important as properties of metals are determined by the
electronic density of states at these points - dispersion relation obtained in the extended-zone
scheme in the empty lattice approximation is identical to the quadratic dispersion relation of
free electrons - the nth band is the part of the free-electron spectrum that falls into the nth
Brillouin zone.
Band structure of electron in a 2-D lattice
Lattice constant a, z electrons per site, N sites total number of electrons
determined by
; giving
is
Figure 5: Special points in 2-D Brillouin zone
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For
, the boundary of the 1st Brillouin zone. So the Fermi surface lies
entirely inside the 1st Brillouin zone.
For
, the boundary of the 1st Brillouin zone. In this case
is larger
than the distance
but smaller than the distance
. Thus, when the lowest-energy states
are filled gradually by electrons in the ground state (as required by the FermiDirac
statistics), the lowest-lying states in the second band becomes occupied before the highestlying states in the first band.
Figure 6: Fermi surface for z=1
Figure 7: Fermi surface for z=2
Figure 8: Band structure for z=2 in 2-D lattice in reduced zone scheme
For the case
, in reduced zone representation, the Fermi surfaces forms discontinuous
structure for the 1st and 2nd band. If the wave vectors are reduced about the points M or X
rather than then the 1st and 2nd bands form continuous Fermi surfaces the 1st band is holelike and the 2nd band is electron-like.
Figure 9: Band structure for z=2 in 2-D lattice in repeated zone scheme
In repeated/periodic zone scheme the nth band is formed of those regions where circles from
at least n different zones overlap.
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Figure 10: z=2 case reduced about the M and X points
The bands thus formed can be electron-like or hole-like depending on whether they enclose a
filled area or an empty area. Note that in a magnetic field electrons will move along a
constant energy surface (remember: magnetic field does not do any work on a moving
charge). For a free electron
Particles in electron-like Fermi surface (Figure 11.b) move in a sense opposite to that in holelike orbits (Figure 11.a).
Figure 11: hole-like and electron-like orbits
Band structure of simple cubic lattice with monatomic basis
Figure 12: band diagram for simple cubic along two symmetry directions
Figure 12.a is for wave vectors along the line connecting the centre = (0, 0, 0) of the
Brillouin zone and X = (/a)(0, 0, 1). The numbers represent the degeneracy of the bands. We
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will calculate the energy of the state associated with the wave vector
Remember the energy is given by
The various bands are:
Band A:
Band B:
Band C:
Band D,E,F,G:
band is 4-fold degenerate
. This
Figure 12.b is for wave vectors along the line
Brillouin zone and R = (/a)(1, 1, 1).
connecting the centre = (0, 0, 0) of the
Assignment problem: Calculate Figure 12b
Effect of weak lattice potential on the free electron dispersion relation
Treat U to be a weak perturbation need not solve the equation can get the result applying
perturbation theory to the U=0 case of free electrons. The results vary appreciably from the
free electron model only near the centre and the edges of the Brillouin zones. Take the
simple example of system of electrons in a very weak 1-D periodic lattice. At the edge of the
Brillouin zone
the condition for Bragg reflection is satisfied. [Recall: Bragg
condition
in 1-D is
.] Hence electrons with wave vector at
the Brillouin zone edge
form standing waves solutions linear superposition of
left moving and right moving waves - two different solutions can be formed from the linear
combination of the left-moving
and the right-moving waves
and
are the symmetric and anti-symmetric solutions respectively. Charge density
associated with
is
Similarly
Density of electrons for
maximum near
i.e. at the lattice sites where the
potential energy is minimum. Similarly density of electrons for
maximum near
i.e. in between the lattice sites where the potential energy is maximum. So the
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energies of the two states at the Brillouin zone edge are no longer degenerate they differ in
energies a band gap opens up of magnitude
just below the gap the state is
and just
above the gap the state is .
Figure 13: potential energy of electrons in a
1D lattice
Figure 14: Energy of symmetric and antisymmetric electronic states at the Bragg plane
Estimate of : Write the potential energy of the electrons as
first order difference in the energy between the two states is
. The
So the band-gap is the Fourier component of the potential energy.
Figure 15: Appearance of band-gap at the Brillouin zone edge
Note: at zone boundaries we have standing waves group velocity
that the slope of the dispersion relation vanishes at the zone boundary.
=0 implying
Figure 16: Band structure of nearly free electrons in extended zone scheme and repeated zone scheme
The constant energy surfaces are spherical in the free-electron approximation. In the case of
electrons in a weak periodic potential, the surfaces are no longer spherical they are distorted
as the Brillouin edge is approached.
Figure 17: constant energy surfaces for (a) free electrons and (b) electrons in a weak periodic potential
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