Week 9

II. Planck distribution

1. Apply the principle to crystal vibrations. Generally, vibration in the crystal is a mix
of waves (with various k’s). For example, the general displacement u(x,t) is given
by the linear superposition of plane waves (k = wave vector)
u(x,t) = SUMk uk exp[i(kx – wkt)],
in the simple mass-spring model, where uk = constant in time. The above
superposition is the result of the wave equation being linear and homogeneous.
As the energy of a component wave ∝ | uk |2 , each uk being constant in time
means that the waves do not interact or exchange energy with each other.
However, when anharmonic terms in the interatomic potential are included,
nonlinear terms will emerge in the equation, invalidating the superposition and
giving uk a time dependence, i.e., uk -> uk(t). In physical terms, energy is
exchanged between waves.
2. Consider a crystal at temperature T. Focus on a wave (wave vector = k). Take it as
the subsystem in thermal equilibrium with the rest of waves (the reservoir).
Recall E = (nk + 1/2) ℏwk. Then the probability of the wave being in the state of
energy E, or having “nk phonons”, is given by

p(nk) ∝ exp[-(nk + 1/2) ℏwk/kBT)] ∝ exp[-(nk ℏwk/kBT)].

3. Normalize the probability and require SUMn p(nk) = 1 (n = 0, 1, 2, ….). It fixes the
overall prefactor in p(nk) giving p(nk) = exp[-(nk ℏwk/kBT)] {1 - exp[-(ℏwk/kBT)]}.
4. The expectation value of phonon number is given by
<nk> = Planck distribution (for the wave with wave vector k)
= SUMnk [nk p(nk)]

= 1/ [exp(ℏwk/kBT) – 1]

III. Density of states (DOS)

1. DOS often arises when calculating physical properties of a crystal. Take the heat
capacity C(T) of an insulating crystal for example. C(T) = dU/dT where U(T) = total
vibrational energy at temperature T. P.2

U(T) = SUMm (<nm> + 1/2) ℏwm (m = wave mode index)

 = SUMm <nm> ℏwm + constant.
The constant above comes from the ground state energy 1/2 ℏwm, which is
unimportant for the calculation of C(T) and will be dropped below. As <nm> is a
function of wm, U(T) can be converted into an integral with respect to w:

U(T) = <nw> ℏw D(w) dw

where D(w) = DOS defined by the total number of wave modes per unit of
frequency at the frequency w, i.e.,
D(w) dw = total number of wave modes in (w - dw/2, w + dw/2).
2. Throughout the chapter, we consider 1D systems and leave the discussion of
2D/3D ones to the textbook. Take a monatomic chain for example. On the
appearance, it looks D(w) = infinity, as shown in the graph below.

Since every point on the dispersion curve denotes a wave mode -> total number
of modes (in dw) = infinity. However, this apparent divergence can be removed by
considering a practical crystal which is finite in size.
3. Let N = total number of cells. For a finite chain, the differential equation for
displacement un(t) has to be supplemented by boundary conditions (BCs), making
it a boundary value problem. Various types of BCs are available. For example,

u0(t) = uN(t) von Neumann or periodic BC;

u0(t) = 0, uN(t) = 0 fixed BC.

4. Generally, properties of a condensed matter system are classified into bulk and
surface ones. Catalysis, for example, is a surface property and studied in surface
science. On the other hand, the heat capacity C(T) is a bulk one as explained
below. It is a measure of vibrational energy increment as T increases. As the
surface to bulk ratio = 2 : N, contribution to C(T) mostly comes from vibrations of
bulk atoms. In particular, in the thermodynamic limit P.3
 where N -> infinity, surface atoms make negligible contribution, so details of BC
are actually irrelevant. On the other hand, for the study of surface properties, BCs
have to be carefully picked to match the realistic surface.
5. We apply the periodic BC and leave the fixed BC (discussed in textbook) to self
reading. Moreover, N is taken to be an even number below, leaving the case of
odd N to students.
u0(t) = uN(t) -> exp(ikNa) = 1.
That is, k is quantized, with

k = 2nπ/Na,

n = -N/2, -N/2 + 1, …, N/2 – 2, N/2 -1.

Conclusion: k is discrete and uniformly distributed in the BZ, with constant

spacing δk = 2π/Na. Overall, there are exactly N in total of discrete k’s or wave
modes.
6. D(w) in 1D is given below. Corresponding to a given dw are two dk’s, as shown in
the graph.

Let dM = wave modes in dw.

dM = D(w) dw
= 2 dk/δk
= 2/δk (dk/dw) dw (change variables k -> w)
= L/π (dk/dw) dw. (Na -> L)
➔ D(w) = L/π (dw/dk)-1.
D(w) is determined by the dispersion. Often, to simplify the calculation, DOS
models developed by Debye and Einstein are applied. P.4
7. Debye proposed the approximate dispersion w(k) = vs w suitable for acoustic
modes, which have a linear dispersion near k = 0. Moreover, the approximate
dispersion is restricted to the 1st BZ, as the exact dispersion, as shown in the
graph.

wD = vs π/a (Debye frequency).

So the dispersion is cut off at wD, giving
w(k) = vs k, w < wD.
Let S(x) = step function defined by S(x < 0) = 0 and S(x > 0) = 1.
➔ D(w) = L/(πvs) S(wD – w).

Note that the inclusion of a cut-off is essential in both the dispersion and DOS.
Without the cut-off, D(w) = L/(πvs) and

With the cut-off, the integral yields

total number of wave modes = N,

as it should.
8. Einstein proposed the approximate dispersion w(k) = wE (a constant called Einstein
frequency), which suits optical modes. It leads to D(w) = N δ(w – wE).

IV. Heat Capacity

1. Thermodynamic behaviors of crystal vibrations can generally be classified into

classical and quantum ones. For a given mode at wave vector k, two energy scales
are involved – thermal energy kBT and quantum energy ℏwk, as graphed below.

P.5
 The ladder shows the various quantized energy states, (n+1/2)ℏwk of the wave,
which is subject to the thermal excitation. Graph A describes the high temperature
regime where the thermal energy kBT >> ℏwk, and Graph B the low temperature
regime where kBT << ℏwk.
2. In the high T regime, <nk> ~ kBT/ℏwk, or the corresponding energy expectation
value <Uk> = <nk> ℏwk ~ kBT. This is known as the equipartition principle in classical
physics, that is, every wave mode carries the same thermal energy. Since kBT >>
ℏwk , the quantum energy scale or quantum effect do not show up. Apply it to
C(T). We get the total vibrational energy U(T) = N kBT, which results in C(T) = N kB
(Dulong-Petit law), where each mode of waves contributes equally (kB) to C(T).
3. In the low temperature regime, since kBT << ℏwk, the thermal energy is insufficient
to excite the mode, giving <nk> ~ exp[-(ℏwk/kBT)] << 1. Such modes do not actively
participate in the thermal physics, although they are solutions of mechanics. We
say these modes are frozen out.
P.6