Short Sample Solutions to the Sample Exam for

(3rd Year Course 6)

Hilary Term 2011

1. [4]
A Lattice is an infinite set of points in space where the environment of any given point is identical to the
enivironment of any other point. The lattice points can be written as

R = n1 a1 + n2 a2 + n3 a3

(here in 3 dimensions) where ni are integers and ai are three linearly independent vectors.
A basis is the set of objects (atoms if one is talking about crystal structure) positioned around each lattice point
which comprises the unit cell. Note, one can define a basis with respect to a primitive, or conventional unit cell.
[8]
Plan view of a conventional unit cell of CaF2 :
1
2

1 3 1 3
4, 4 4, 4
Ca= y
1 1
a 2 2

1 3 1 3
F= 4, 4 4, 4

x
1
2
a

Unlabeled atoms are at z = 0 and z = a.

Lattice planes (1 1 0)

Lattice planes (2 0 0)
 2

Lattice planes (4 0 0)

[9]
This is an application of Bragg’s law

2d(hkl) sin θ = λ

Here θ = 21.0 degrees (the full deflection is 42 degrees), and d(200) = a/2. Thus we have a = λ/ sin 21o = .558nm
the lattice constant for the cubic unit cell.
fcc crystals do not produce a (1 1 0) scattering because of the selection rules (that the three (hkl) indices must be
all odd or all even). To see this explicitly we write a basis for the atoms in the FCC unit cell. This basis within
the conventional unit cell (ie, with respect to a cubic lattice) is given (in units of the cubic lattice constant)
by the four points (x, y, z) given by R1 = (0, 0, 0), R2 = (1/2, 1/2, 0), R3 = (1/2, 0, 1/2), R4 = (0, 1/2, 1/2).
The structure factor for any incident plane wave with wavevector k corresponding to miller indices (hkl) will
have a factor of
4
f cc
X X
S(hkl) = e2πi(Rd ·k) = e2πi(hxd +kyd +lzd ) = 1 + eiπ(h+k) + eiπ(h+l) + eiπ(k+l)
d=1 d

for any fcc structure. As stated above, this sum vanishes unless the three miller indices are all odd or all even.
Hence (1 1 0) does not produce a peak.
[4]
Generally the structure factor will be given by
X
S(hkl) = fd e2πi(hxd +kyd +lzd )
d

where the sum over d is the sum over all atoms in the unit cell, fd is the form factor for atom of type d and
(xd , yd , zd ) are the coordinates of atom d in the unit cell.
For Ca, one obtains
Ca f cc
S(hkl) = S(hkl) fCa

For CaF2 one obtains

h π  i
CaF2 f cc
S(hkl) = S(hkl) fCa + 2 cos (h + k + l) fF
2
 3

For X-ray scattering f is positive and roughly proportional to the atomic number Z of the atom (ZF = 9, ZCa =
20, so fCa is roughly twice as big as fF .
For CaF2 the interference between the Ca and F terms is destructive for (2 0 0) but constructive for (4 0 0).
When the interference is destructive, the two terms may very nearly cancel.
The actual observed scattered Xray intensity is proportional to |Shkl |2 times a multiplicity factor (for powder
diffraction). This multiplicity factor (8) is the same for (2 0 0) and (4 0 0) and the same for Ca and CaF2 .
Thus
Ca Ca 2
I(200) I(400)

20
CaF2
>> 1 and CaF2
≈
I(200) I(400) 38

(with the last approximation is assuming f ∼ Z and assuming that lattice constants of Ca and CaF2 are similar
and assuming that there is no strong dependence of the scattering on wavelength. With the same assumptions
one would obtain 100 for the first ratio, although this depends sensitively on the precise values of f and should
not be taken too seriously).
 4

2. [6]
A phonon is a quantum of vibration in a solid analogous to a photon being a quantum of light. ((begin rant)
Using the phrase “quantum of vibrational energy” is discouraged the same way one would not say that a photon
is a quantum of light energy you just say “a quantum of light”– being that the phonon/photon carries other
quantum numbers as well as energy (end rant)).
Phonon dispersion is most easily measured with inelastic neutron scattering. In short, this exploits energy and
momentum conservation. A neutron is fired into the crystal with known energy and momentum, it excites a
phonon and is measured coming out of the crystal. Assuming a single phonon is excited, the change in neutron
energy gives the energy of the phonon and the change in neutron momentum gives the phonon momentum.
[10]
The classical equations of motion for the pth atom are
X
M ẍp = Fp = Cn (xn+p − xp )
n

Note, we must have Cn = C−n by Newton’s third law.

Using the usual ansatz xp = Aeiωt−ikpa we obtain
X X
−M ω 2 = Cn (e−ikna − 1) = 2Cn (cos(kna) − 1)
n n>0

Using 1 − cos(x) = 2 sin2 (x/2) we obtain

4 X
ω2 = Cn sin2 (nka/2)
M n>0

Square-rooting this gives the desired expression. Backing up a step, we write this as
2 X
ω 2 (k) = Cm (1 − cos(kma))
M m>0

Now multiplying by cos(kna) and integrating from −π/a to π/a gives

π/a Z π/a
2 X
Z
dk ω 2 (k) cos(nka) = Cm dk(1 − cos(kma)) cos(nka)
−π/a M m>0 −π/a

Now using the orthogonality of cosines

Z π/a
2π
dk cos(nka) cos(mka) = δ|n|,|m|
−π/a 2a

we get
π/a
2 π
Z
dk ω 2 (k) cos(nka) = − Cn
−π/a Ma

which gives the desired result.

[4]
Expand for small kna. We obtain
4 X 1 X
ω2 = Cn sin2 (nka/2) = Cn n2 k 2 a2
M n>0 M n>0

We now use the fact that Cn falls off rapidly with n such that the sum over n converges. We then obtain
s
a2 X
ω=k Cn n2
M n>0
 5

where ω = ku thus gives the desired result.

s
a2 X
u= Cn n2
M n>0

[5]
A sketch of the dispersion curve is given in (a) for C1 > 0 and all other Cn = 0. In (b) dispersion curve is
shown for C1 > 0 and C2 > 0 with all other Cn = 0. In (c) dispersion curve is given where Cn ∼ exp(−nb)
where roughly δk is given by bπ/a. (To see this, note that Cn decays at a distance roughly a/b. This form of
Cn can also be calculated exactly.). Roughly, inclusion of a nonzero Cn for each n gives an nth fourier mode to
the dispersion curve. (Although ω is actually the square root of a fourier series)
 6

3. [6]
The Fermi Energy EF is the chemical potential at zero temperature. Roughly you can think of this as the energy
to add the next electron. However, you have to be careful in the case when you have exactly enough electrons to
completely fill a band. In this case the chemical potential sits mid-gap at zero temperature. (So more properly
it is the average of the energy to add the next electron and the last electron) . The Fermi Temperature TF is
just EF /kb with kb Boltzmann’s constant.
[13]
The number of electronic states with energy lower than some absolute value of momentum k0 is given by

d2 k 2A
Z
N (k0 ) = 2A = πk 2 .
|k|<k0 (2π)
2 (2π)2 0

where the prefactor of 2 is from the spin and A is the area (two dimensional volume). With k0 = h̄2 k02 /(2m)
we have

g = dN/d = (dN/dk0 )(dk0 /d) = Am/(πh̄2 )

which is independent of energy.

∞
Am
Z
N= dE/(e(E−µ)/kb T + 1)
πh̄2 0

Using x = (e(E−µ)/kb T + 1) we have kb T log(x − 1) + µ = E so dE = (kb T /(x − 1))dx. We then can write

Am ∞ kb T 1
Z
N= dx
πh̄2 e−µ/(kb T ) +1 x − 1 x
or
∞
N πh̄2 ∞ ∞   
1 1 1 x − 1 
Z Z
= dx = dx − = log
Amkb T e−µ/(kb T ) +1 x(x − 1) e−µ/(kb T ) +1 x−1 x x  −µ/(k T )
e b +1

So
nπh̄2
 
exp = 1 + eµ/(kb T )
mkb T

with n = N/V . This quickly simplifies to the desired

µ = kb T log exp(nπh̄2 /mkb T ) − 1

[6]
Using the result just derived we can take the limit of T becoming small and obtain

nπh̄2
lim µ =
T →0 m
which defines the fermi energy. Alternately we could use the fact that the density of states is constant. So at
T = 0, we have N = gEF = AmEF /πh̄2 which gives the same result.
For a typical three dimensional metal, because the density of electrons is very high, EF is very large – in
the electron volt range, which corresponds to thousands of kelvin – much higher than room temperature. For
many purposes room temperature T , being much less than EF can be approximated as essentially zero. In
approximating the Fermi-dirac formula, one does not approximate T as zero, but neglects the dependence of µ
on T . In other words, we have

µ = µ(T = 0) + O(T /EF )

 7

and the correction is neglected (noting that µ(T = 0) = EF ). In fact, a more detailed calculation show that the
correction to the chemical potential is order (T /EF )2 . To see this we note that the chemical potential at any
temperature the first equation given in this problem
Z ∞
g(E)
N= dE (E−µ)/k T
0 e b +1

sets the chemical potential. At T = 0 the fermi factor becomes a step function (and µ = EF ). As the temperature
is raised, the step function becomes a smoother step. But close to the fermi energy, the increase of the fermi
function above EF is equal to the decrease below EF so to linear order in T /EF there is no change in N for
fixed chemical potential, and correspondingly to linear order in T the chemical potential does not change for
fixed N .
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4. [6]
In simple band theory of electrons (i.e, electrons that do not interact with each other) an insulator occurs when
the number of electrons is such that a band is completely filled and there is an energy gap to the next band.
Thus there are no low energy excitations of electrons possible and an applied electric field cannot change the
velocity of the electrons, hence no current flows and one has an insulator.
[3]
The matrix element between a plane-wave state of momentum k and momentum k 0 is given by

hk 0 |V (x)|ki

If the periodic potential is of the form given

V (x) = V0 + VG e−iGx + V−G eiGx

then the matrix element is nonzero only if k = k 0 (giving the V0 term) or

k = k0 ± G

giving the VG and V−G terms respectively.

In the nearly free electron model, we are now trying to calculate the energy of a plane wave perturbed by V .
Let us try the usual perturbation theory expansion
X |hk 0 |V |ki|2
k = 0k + hk|V |ki + + ...
0k − 0k0
k 6=k
0

where 0k = h̄2 k 2 /(2m).

The leading term hk|V |ki gives V0 independent of k (and is therefore not interesting). The next order term
requires that k 0 = k ± G (note the sum forbids k = k 0 ). However, in order for the term to be significantly large,
it must also have a small denominator, i.e., k ≈ k0 which in the 1d model only occurs for k ≈ ±k 0 . The only
way this can occur is when k is close to ±G/2 and k 0 is close to ∓G/2. It is thus valid to keep only these two
wavevectors in the analysis of the problem as claimed. Note that when k is exactly ±G/2, perturbation theory
breaks down because of the divergent denominator and one must resort to degenerate perturbation theory. As
such, one first solves the problem within the space of states having degenerate energies. This again tells us that
we should keep k = ±G/2 to a first approximation.
[10]
We write our Hamiltonian as H = H0 + V with H0 being the usual kinetic term and V the potential. We have
the ansatz

|ψk i = A|ki + B|k − Gi

with the assumption that k is near the zone boundary G/2. (Note I have used a different normalization to write
a normalized ket rather than just an exponential). We will use

H0 |ki = 0k |ki

with 0k = h̄2 k 2 /(2m) and

V |ki = V0 |ki + VG |k − Gi + V−G |k + Gi

These equations are true for arbitrary k.

We write the schroedinger equation as

H|ψk i = (H0 + V )|ψk i = k |ψk i

Using the above equations we then rewrite this as

AV−G |k + Gi + (A0k + BV−G + AV0 )|ki + (B0k−G + AVG + BV0 )|k − Gi + BVG |k − 2Gi = k (A|ki + B|k − Gi)
 9

At this point, we need to ”project” back to our subspace of states which are only those near the zone boundaries
k = ±G/2 (i.e, to the space of |ki and |k − Gi only). The valid argument for doing this is that given above –
that other terms will have energy denominators in perturbation theory and will therefore be much smaller. The
mathematical way to do this is to obtain two equations by taking inner products with hk| and hk − G| to obtain

(A0k + BV−G + AV0 ) = k A

(B0k−G + AVG + BV0 ) = k B

These can be rewritten as an eigenvalue equation

 0    
k + V0 V−G A A
= k
VG 0k−G + V0 B B

We can calculate the eigenvalue for any k (so long as we keep k close to G/2 as we assumed). However, it
becomes much easier if we consider only k = G/2. We then have 0k = 0k−G = h̄2 k 2 /(2m). The eigenvalues of
this matrix then simplify to

(k=G/2) = V0 + 0k ± |VG |

as claimed (where we have used VG = (V−G )∗ ) here.

The first term is the uniform potential that gives just an overall shift of energy (or chemical potential). The
second term is the free electron plane wave energy. The final term is the gap that opens up at the zone boundary
(full gap is 2|VG |) due to the periodic potential. If the number of electrons is such that the band is precisely
filled, the size of |VG | will determine if this is a semiconductor or an insulator. If the band is not precisely filled,
we will have a metal (at least in simple band theory approximation).
[6]
Germanium, Silicon, and Diamond all have the same crystal structure with two tetravalent atoms per primitive
unit cell – a number which can precisely fill four bands (of two spins each). In the case of diamond, the periodic
potential is stronger, so the gap between bands is larger and one obtains an insulator. For Si and Ge, there is
still a gap, but it is smaller (hence they are semiconductors). A rough reason why the potential is stronger for
carbon is that the Coulomb potential is unscreened by inner atomic shells.