Contents

1 Introduction 2
1.1 Goals in this course . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 Statistical mechanics of free Fermi gas . . . . . . . . . . . . 2
1.2.1 T = 0 Fermi sea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2.2 T > 0 Free energy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2.3 Avg. fermion number. . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2.4 Fermi gas at low T. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2.5 Classical limit. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.3 Second quantization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.3.1 Symmetry of many-particle wavefunctions . . . . . . . . . . . 9
1.3.2 Field operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.3.3 2nd-quantized Hamiltonian . . . . . . . . . . . . . . . . . . . . . . 13
1.3.4 Schrödinger, Heisenberg, interaction representations . . . . 15
1.4 Phonons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.4.1 Review of simple harmonic oscillator quantization . . . . . 17
1.4.2 1D harmonic chain . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1.4.3 Debye Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.4.4 Anharmonicity & its consequences . . . . . . . . . . . . . . . . . 22

1
1 Introduction
1.1 Goals in this course
These are my hopes for the course. Let me know if you feel the course
is not fulfilling them for you. Be free with your criticism & comments!
Thanks.
• Teach basics of collective phenomena in electron systems
• Make frequent reference to real experiment and data
• Use 2nd quantized notation without field-theoretical techniques
• Get all students reading basic CM journals
• Allow students to practice presenting a talk
• Allow students to bootstrap own research if possible

1.2 Statistical mechanics of free Fermi gas

1.2.1 T = 0 Fermi sea
Start with simple model of electrons in metal, neglecting e− − e− interac-
tions. Hamiltonian is
X h̄2∇2j
Ĥ = − , j = 1, . . . N particles (1)
j 2m
Eigenstates of each −(h̄2∇2/2m) are just plane waves eik·r labelled by k,
with ki = 2πni/Li in box with periodic B.C. Recall electrons are fermions,
which means we can only put one in each single-particle state. Including
spin we can put two particles (↑↓) in each k-state. At zero temperature
the ground state of N -electron system is then formed by adding particles
until we run out of electrons. Energy is εk = h̄2k 2/2m, so start with
two in lowest state k = 0, then add two to next states, with kx or ky
2
or kz = 2π/L, etc. as shown. Energy of highest particle called “Fermi
energy” εF , magnitude of corresponding wave vector called kF . Typical
Fermi energy for metal εF ' 1eV ' 104K. At T = 0 only states with
k < kF occupied (Fermi “sea” or Fermi sphere), so we can write density
of electrons as 2*# occupied states/Volume (2 is for spin):
kF
2 X Z d3k 1 Z kF 2 kF3
n= 3 ' 2 k<k = 2 0 k dk = 2 (2)
L k=0 F (2π)3 π 3π
so
2 1/3 h̄2(3π 2n)2/3
kF = (3π n) or εF = (3)
2m
in other words, nothing but the density of electrons controls the Fermi
energy.

Figure 1: States of Fermi gas with parabolic spectrum, ε = k 2 /2m.

The total ground state energy of the Fermi gas must be of order εF ,
since there is no other energy in the problem. If we simply add up the
energies of all particles in states up to Fermi level get

2 2
E 1 Z k
F 2  h̄ k  h̄2kF5
= dk k   = (4)
L3 π 2 0 2m 10π 2m
and the ground state energy per particle (N = nL3 is the total number)
is
E 3
= εF . (5)
N 5
3
1.2.2 T > 0 Free energy.
Reminder: partition function for free fermions in grnd conical ensemble is
Z = Tr e−β(Ĥ−µN̂ ) (6)
X
= hn1, n2...n∞ |e−β(Ĥ−µN̂ )|n1, n2...n∞ i (7)
n1 ,n2 ...nk∞
X P
= hn1, n2...n∞ |e−β( i [εini −µni ]) |n 1 , n2 ...n∞ i (8)
n1 ,n2 ...n∞

where i labels single-fermion state, e.g. i = k, σ, and ni runs from 0 to

1 for fermions. Since many-fermion state in occ. no. representation is
simple product: |n1, n2...n∞ i = |n1i|n2i...|n∞i, can factorize:
   
X X
Z= e−β[ε1 n1−µn1 ] · · ·  e−β[ε∞n∞−µn∞ ] , (9)
n1 n∞
so
 
Z= Π∞
i=0 1+e −β(εi −µ)
(10)
Since the free energy (grand canonical potential) is Ω = −kB T log Z, we
get
 
P∞ −β(εi −µ)
Ω = −kB T i=1 log 1+e (11)

1.2.3 Avg. fermion number.

We may want to take statistical averages of quantum operators, for which
we need the statistical operator ρ̂ = Z −1 e−β(Ĥ−µN̂ ). Then any operator
Ô has an expectation value hÔi = Tr(ρ̂Ô). For example, avg. no. of
particles

hN̂ i = Tr(ρN̂ ) (12)

Tr(e−β(Ĥ−µN̂ )N̂ )
= (13)
Tr(e−β(Ĥ−µN̂ ))
4
Now note this is related to derivative of Ω wrt chem. potential µ:
∂Ω ∂ log Z −kB T ∂Z
= −kB T = (14)
∂µ ∂µ Z ∂µ
−1
= Tr(ρN̂ ) = −hN̂ i (15)
Z
and using Eq. 11, we see
∞
X 1 ∞
X
hN̂ i = β(ε −µ)
≡ n 0
i (16)
i=1 1 + e i i=1
where ni0 is the avg. number of fermions in a single-particle state i in
equilibrium at temperature T . If we recall i was a shorthand for k, σ, but
εk doesn’t depend on σ, we get Fermi-Dirac distribution function
1
n0kσ = (17)
1 + eβ(εk−µ)

1.2.4 Fermi gas at low T.

Since the Fermi energy of metals is so high (∼ 104K), it’s important to
understand the limit kB T  εF , where the Fermi gas is nearly degen-
erate, and make sure the classical limit kB T  εF comes out right too.
Let’s calculate, for example, the entropy and specific heat, which can be
obtained from the thermodynamic potential Ω via the general thermody-
namic relations    
∂Ω ∂S
S = −   ; CV = T   (18)
∂T V,µ ∂T V,µ
From (11) and (16), and including spin, we have
X  
Ω = −2kB T log 1 + e−β(εk −µ)
k
Z  
= 2kB T L3 dεN (ε) log 1 + e−β(ε−µ)
⇒ !
CV 1 Z∞ −∂f
cV ≡ 3
=2 dεN (ε) (ε − µ)2
L kB T 0 ∂ε
Z !
1 ∞ −∂f 2
= 2 dξ N (ξ) ξ (19)
kB T −µ ∂ξ
5
 X
where I introduced the density of k-states for one spin N (ε) = L−3 kδ(ε−
εk). The Fermi function is f (ε) = 1/(1+exp β(ε−µ)), & I defined shifted
energy variable ξ = ε−µ. In general, the degenerate limit is characterized
by k sums which decay rapidly for energies far from the Fermi surface, so
the game is to assume the density of states varies slowly on a scale of the
thermal energy, and replace N (ε) by N (εF ) ≡ N0. This type of Sommer-
feld expansion1 assumes the density of states is a smoothly varying fctn.,
i.e. the thermodynamic limit V → ∞ has been taken (otherwise N (ε) is
too spiky!). For a parabolic band, εk = h̄2k 2/(2m) in 3D, the delta-fctn.
can be evaluated to find2
 
3 n  ε 1/2
N (ε) = θ(ε). (22)
2 εF εF
This can be expanded around the Fermi level:3
1
N (ξ) = N (0) + N 0 (0)ξ + N 00 (0)ξ 2 + . . . (24)
2
(In a horrible misuse of notation, N (0), N (εF ), and N0 all mean the
1
If you are integrating a smooth function of ε multiplied by the Fermi function derivative −∂f /∂ε, the derivative
restricts the range of integration to a region of width kB T around the Fermi surface. If you are integrating something
times f (ε) itself, it’s convenient to do an integration by parts. The result is (see e.g. Ashcroft & Mermin appendix
C)

Z ∞ Z µ ∞
X d2n−1
dεH(ε)f (ε) = dεH(ε) + an (kB T )2n H(ε)|ε=µ (20)
−∞ −∞ n=1
dε2n−1


where an = 2 − 1/22(n−1) ζ(2n) (ζ is Riemann ζ fctn., ζ(2) = π 2 /6, ζ(4) = π 4 /90, etc.).
2
Here’s one way to get this:
Z √ Z 2   √  1/2
X d3 k dε −1 2mε k dk m 2mε 3 n ε
−3
N (ε) = L δ(ε − εk ) → 3
| | δ(k − ) = 2 2 δ(k − ) = (21)
(2π) dk h̄ 2π h̄ k h̄ 2 εF εF
k

3
When does the validity of the expansion break down? When the approximation that the density of states is a
smooth function does, i.e. when the thermal energy kB T is comparable to the splitting between states at the Fermi
level,
h̄2 kF δk δk a
δεk |εF ' ' εF ' εF , (23)
m kF L
where a is the lattice spacing and L is the box size. At T = 1K, requiring kB T ∼ δε, and taking εF /kB ' 104 K
says that systems (boxes) of size less than 1µm will “show mesoscopic” effects, i.e. results from Sommerfeld-type
expansions are no longer valid.

6
 Figure 2: Density of states for parabolic spectrum, ε = k 2 /2m

density of states at the Fermi level). The leading order term in the low-T
specific heat is therefore found directly by scaling out the factors of T in
Eq. (19):
   
1 Z ∞ −∂f  2 Z ∞ −∂f  2
cV ' 2kB N0 −∞
dξ  ξ = 2kB T −∞
dx  x (25)
T ∂ξ | {z
∂x }

π 2/3
So
2π 2
cV ' N0kB T + O(T 3). (26)
3
This is the famous linear in temperature specific heat of a free Fermi
gas. 4

4
Note in (26), I extended the lower limit −µ of the integral in Eq. (19) to −∞ since it can be shown that the
chemical potential is very close to εF at low T . Since we are interested in temperatures kB T  εF , and the range
in the integral is only several kB T at most, this introduces neglible error.
Why:
At T =0, the Fermi function n0k → step function θ(µ − εk ), so we know µ(T = 0) must just be the Fermi energy
εF = h̄2 (3π 2 n)2/3 /2m.
∞
X
N −3
n = = 2L n0k
L3
k
Z
= 2 dεN (ε)f (ε)
Z µ
π2
' dεN (ε) + (kB T )2 N 0 (ε)|ε=µ (continued on next page)
−∞ 6

7
1.2.5 Classical limit.
I won’t calculate the classical limit. All the standard results for a Boltzman
statistics gas, e.g. cV (T  εF ) = (3/2)N kB follow immediately from
noticing that the Fermi function reduces to the Boltzman distribution,
f (ε) → e−β(ε−µ), T → ∞. (27)
(You will need to convince yourself that the classical result µ/(kB T ) →
−∞ is recovered to make this argument.)

1.3 Second quantization

The idea behind the term ”second quantization” arises from the fact that in
the early days of quantum mechanics, forces between particles were treated
classically. Momentum, position and other observables were represented
by operators which do not in general commute with each other. Particle
number is assumed to be quantized as one of the tenets of the theory, e.g.
Einstein’s early work on blackbody radiation.
At some point it was also realized that forces between particles are also
quantized because they are mediated by the exchange of other particles. In
Schrödinger’s treatment of the H-atom the force is just the classical static
Coulomb force, but a more complete treatment includes the interaction
of the H-atom and its constituents with the radiation field, which must
itself be quantized (“photons”). This quantization of the fields mediat-
ing the interactions between matter particles was referred to as “second”
quantization. In the meantime, a second-quantized description has been
developed in which both “matter fields” and “force fields” are described
Z εF
π2
' dεN (ε) +(µ − εF )N (εF ) + (kB T )2 N 0 (ε)|ε=µ
−∞ 6
| {z }
n
π2 N 0 (εF )
⇒ µ ' εF − (kB T )2
6 N (εF )

Since N 0 /N is typically of order 1/ε2F , corrections are small.

8
by second-quantized field operators. In fact, modern condensed matter
physics usually does go backwards and describe particles interacting via
classical Coulomb forces again,5 but these particles are described by field
operators. Once the calculational rules are absorbed, calculating with
the 2nd-quantized formalism is easier for most people than doing 1st-
quantized calculations. They must, of course, yield the same answer, as
they are rigorously equivalent. I will not prove this equivalence in class,
as it is exceedingly tedious, but merely motivate it for you below. I urge
you to read the proof once for your own edification, however.6

1.3.1 Symmetry of many-particle wavefunctions

Quantum mechanics allows for the possibility of indistinguishable parti-
cles, and nature seems to have taken advantage of this as a way to con-
struct things. No electron can be distinguished from another electron,
except by saying where it is, what quantum state it is in, etc. Inter-
nal quantum-mechanical consistency requires that when we write down
a many-identical-particle state, we make that state noncommittal as to
which particle is in which single-particle state. For example, we say that
we have electron 1 and electron 2, and we put them in states a and b re-
spectively, but exchange symmetry requires (since electrons are fermions)
that a satisfactory wave-function has the form
Ψ(r1, r2) = A[(ψa (r2)ψb(r1) − ψa (r1)ψb(r2)]. (28)

If we have N particles, the wavefunctions must be either symmetric or

antisymmetric under exchange:7
ΨB (r1 . . . ri . . . rj . . . rN ) = ΨB (r1 . . . rj . . . ri . . . rN ) Bosons (29)
ΨF (r1 . . . ri . . . rj . . . rN ) = −ΨF (r1 . . . rj . . . ri . . . rN ) Fermions (30)
5
Q: when does this approximation break down?
6
See, e.g. Fetter & Wallecka, Quantum Theory of Many-Particle Systems
7
Recently, a generalization of Bose & Fermi statistics to particles called anyons has been intensely discussed.
Under exchange an anyon wavefunction behaves as ΨA (r1 . . . ri . . . rj . . . rN ) = eiθ ΨA (r1 . . . rj . . . ri . . . rN ) for some
0 ≤ θ ≤ 2π.

9
 Given a set of single-particle wave functions φEi (r), where Ei is a quan-
tum number, e.g. energy, we can easily construct wave fctns. which satisfy
statistics, e.g.
!1/2
B n1!n2! · · · n∞ ! X
Ψ F
n1 ...n∞ (r1, . . . rN ) = (±1) sgnP P ΠN
i=1 φEi (ri ) (31)
N! P∈{E1 ,E2 ...EN }

Remarks on Eq. (31):

• sum all permutations of the Ei ’s in product φE1 (r1)φE2 (r2) . . . φEN (rN ).8
• # distinct Ei ’s occuring may be less than N , some missing because
of multiple occupation in boson case. Example:
particles

ΨB20100...0 (r1 , r2 , r3 ) =
1
= √ {φE1 (r1 )φE1 (r2 )φE3 (r3 ) +
3
+φE3 (r1 )φE1 (r2 )φE1 (r3 ) +
+φE1 (r1 )φE3 (r2 )φE1 (r3 )}

Fig. 2. Possible state of 3 noninteracting Bose

• Completely antisymmetric Fermionic wavefunction called Slater de-

terminant:
 1/2 φE (r1) . . . φEmax (r1)
min
1 .
.. ...
Ψn1 ...n∞ (r1, . . . rN ) =   (32)
N!
φEmin (rN ) . . . φEmax (rN )
where there are N eigenvalues which occur between Emin and Emax ,
inclusive, corresponding to N occupied states.

8
You might think the physical thing to do would be to sum all permutations of the particle labels. This is correct,
but actually makes things harder since one can double count if particles are degenerate (see example of 3 bosons
below.) The normalization factor is chosen with the sum over all permutation of the Ei ’s in mind.

10
1.3.2 Field operators
2nd quantization is alternative way of describing many body states. We
describe a particle by a field operator
X
ψ̂(r) = aiφEi (r) (33)
i
where i runs over the quantum numbers associated with the set of eigen-
states φ, ai is a “coefficient” which is an operator (I’m going to neglect
the hats (ˆ ) which normally denote an operator for the a’s and a†’s), and
φEi is a “1st-quantized” wavefunction, i.e. a normal Schrödinger wave-
function of the type we have used up to now, such that (for example)
HφEi = Ei φEi . Now we impose commutation relations
 
† 0
ψ̂(r), ψ̂ (r ) ±
= δ(r − r0) (34)
   
0 † † 0
ψ̂(r), ψ̂(r ) ±
= ψ̂ (r), ψ̂ (r ) ±
= 0, (35)
which implies
[ai, a†j ]± = δij ; [ai, aj ]± = [a†i , a†j ]± = 0. (36)
The upper sign is for fermions and the lower for bosons in Eqs. (35) and
(36).
Now construct many-body states from vacuum (no particles) |0i. a called
annihilation operator, a† creation operator (see below).
Examples & comments (all properties follow from commutation rela-
tions):
Bosons:

• one particle in state i: a†i |0i ≡ |1ii

• annihilate vacuum ai|0i = 0
• (Bosons)9 a†i a†i |0i ≡ |2ii
9
Analogous state for fermions is zero, by commutation relations-check!

11
 • (Bosons) two in i and one in j: a†i a†i a†j |0i ≡ |2ii|1ij
• a†i ai ≡ n̂i is number operator for state i.
Proof: (bosons)

(a†i ai )|nii = (a†i ai )(a†i )n |0i

= a†i (1 + a†i ai )(a†i )n−1|0i = |nii + (a†i )2ai (a†i )n−1|0i
= 2|nii + (a†i )3 ai (a†i )n−2|0i . . . = n|nii

Similarly show (bosons):10

• a†i |nii = (n + 1)1/2|n + 1ii

• ai|nii = n1/2|n − 1ii

• many-particle state
 1/2
1
  (a†1)n1 (a†2)n2 · · · |0i ≡ |n1, n2 . . . n∞i (37)
n1!n2! . . . n∞!

? occupation numbers specify state completely, exchange symmetry

included due to commutation relations! (normalization factor left for
problem set)

Fermions

• Anticommutation relations complicate matters, in particular note

1
a2 = (a†)2 = 0 ⇒ ni = (Pauli principle) (38)
0
10
By now it should be clear that the algebra for the bosonic case is identical to the algebra of simple harmonic
oscillator ladder operators.

12
 • so
a† |0i = |1i a|1i = |0i
(39)
a†|1i = 0 a|0i = 0
• many-particle state
(a†1)n1 (a†2)n2 · · · |0i ≡ |n1, n2 . . . n∞i (40)
? note normalization factor is 1 here.

• action of creation & annilation operators (suppose ns = 1):

as| . . . ns . . .i = (−1)n1+n2 +...ns−1 (a†1)n1 · · · asa†s · · · (a†∞ )n∞ |0i
= (−1)n1+n2 +...ns−1 (a†1)n1 · · · (1 − a †
s a
| {z }
s ) · · · (a † n∞
∞) |0i
=0

= (−1)n1+n2 +...ns−1 | . . . ns − 1 . . .i

also
as| . . . 0 . . .i = 0 (41)
and similarly

(−1)n1+n2 +...ns−1 | . . . ns + 1 . . .i ns = 0


a†s| . . . ns . . .i =
 0
(42)
ns = 1

1.3.3 2nd-quantized Hamiltonian

? Point: Now “it can be shown”11 that state vector
X
|Ψ(t)i = f (n1, n2 . . . n∞, t)|n1, n2 . . . n∞i (43)
n1 ,n2 ...n∞

11
Normally I hate skipping proofs. However, as mentioned above, this one is so tedious I just can’t resist. The
bravehearted can look, e.g. in chapter 1 of Fetter and Wallecka.

13
satisfies the Schrödinger equation (our old friend)
∂
ih̄ |Ψ(t)i = Ĥ|Ψ(t)i (44)
∂t
if we take the ”2nd-quantized” form of Ĥ
X † 1 X † †
Ĥ = ai hi|T |jiaj + a a hij|V |k`ia`ak (45)
ij 2 ijk` i j
Z
= d3rψ̂ † (r)T (r, ∇r)ψ̂(r) (46)
1Z Z 3 3 0 †
+ d r d r ψ̂ (r)ψ̂ † (r0)V (r, r0)ψ̂(r0)ψ̂(r) (47)
2
where the 1st quantized Hamiltonian was H = T + V .
Translationally invariant system
It may be more satisfying if we can at least verify that this formalism
“works” for a special case, e.g. translationally invariant systems. For
such a system the momentum k is a good quantum number, so choose
single-particle plane wave states
φi(r) = φkσ (r) = L−3/2eik·r uσ , (48)
 
where uσ is a spinor like u↓ = 01 , etc. 1st quantized T is −∇2/(2m),12
so 2nd-quantized kinetic energy is
 
2
X X k  †
T̂ ≡ a†i hi|T |jiaj =   akσ akσ . (49)
ij kσ 2m
Since we showed a†kσ akσ is just number operator which counts # of par-
ticles in state kσ, this clearly just adds up the kinetic energy of all the
occupied states, as it should. For general two-particle interaction V , let’s
assume V (r, r0) = V (r − r0) only, as must be true if we have transl.
invariance. In terms of the Fourier transform
1 Z 3 iq·r
V (q) = 3 d r e V (r) (50)
L
12
I’ll set h̄ = 1 from here on out, unless required for an honest physical calculation.

14
we have (steps left as exercise)
1 X
V̂ = a†kσ a†k0+qσ0 V (q)ak0σ ak+qσ (51)
2 k,k0 ,q
σ,σ 0

1.3.4 Schrödinger, Heisenberg, interaction representations

Here we just give some definitions & reminders on different (equivalent)
representations of quantum mechanics. In different reps., time depen-
dence is associated with states (Schrödinger), operators (Heisenberg), or
combination (interaction).

• Schrödinger picture

state |ψ̂S (t)i, operators ÔS 6= ÔS (t)

∂
i |ψ̂S (t)i = Ĥ|ψ̂S (t)i
∂t
has formal solution
|ψ̂S (t)i = e−iĤ(t−t0 )|ψ̂S (t0)i (52)

Note Ĥ hermitian ⇒ time evolution operator Û ≡ eiĤ(t−t0 ) is uni-

tary.
• Interaction picture (useful for pert. thy.)
Ĥ = Ĥ0 + Ĥ 0 (where Ĥ0 usually soluble)

Def. in terms of Schr. picture: |ψ̂I (t)i = eiĤ0 t|ψ̂S (t)i

ÔI (t) = eiĤ0 tÔS e−iĤ0 t

∂
⇒i |ψ̂I (t)i = Ĥ 0 (t)|ψ̂I (t)i
∂t
15
 with Ĥ 0 (t) = eiĤ0 tĤ 0 e−iĤ0 t
Remarks:
– states and ops. t-dependent in interaction picture, but time de-
pendence of operators very simple, e.g.
X
Ĥ0 = εka†kak
k

∂
i akI (t) = eiĤ0 t[ak, Ĥ0]e−iĤ0 t
∂t
= εkakI (t)

⇒ akI (t) = ake−iεk t

– Time evolution operator determines state at time t:
|ψ̂I (t)i = Û (t, t0)|ψ̂I (t0)i
From Schrödinger picture we find
Û (t, t0) = eiĤ0 t e−iĤ(t−t0 )e−iĤ0 t0 (53)
(Note ([Ĥ, Ĥ0] 6= 0!)
• Heisenberg picture
state |ψ̂H i t-independent,
operators ÔH (t) = eiĤt ÔS e−iĤt
so operators evolve according to Heisenberg eqn. of motion
∂
i ÔH (t) = [ÔH (t), H] (54)
∂t
? Note–compare three reps. at t = 0:
|ψ̂H i = |ψ̂S (0)i = |ψ̂I (0)i (55)
ÔS = ÔH (0) = ÔI (0) (56)
16
1.4 Phonons
1.4.1 Review of simple harmonic oscillator quantization
I will simply write down some results for the standard SHO quantization
from elementary QM using “ladder operators”. We consider the Hamilto-
nian
p2 K
H= + q2 (57)
2M 2
and extract the relevant dimensions by putting
K
ω2 =
M
 

M ω 1/2
ξ = q
h̄
∂
−i = p(h̄M ω)−1/2 (58)
∂ξ
so  
h̄ω  ∂ 2 2
H= − + ξ . (59)
2 ∂ξ 2
We recall soln. goes like e−ξ
2 /2
Hn (ξ), where Hn are Hermite polynomials,
and that eigenvalues are
En = h̄ω(n + 1/2) (60)
Define ladder operators a, a† as
 
1 ∂
a = √ ξ +  (61)
2 ∂ξ

1 ∂
a† = √ ξ −  (62)
2 ∂ξ
Ladder ops. obey commutation relations (check)
[a, a†] = 1 ; [a, a] = 0 ; [a†, a†] = 0 (63)

17
 x eq
l
eq
x l+1

K K K

xi
x i+1

Figure 3: Linear chain with spring couplings K. Dynamical variables are qi ≡ xi − xeq
i

& then H may be written (check)

 
1
H = h̄ω a†a +  . (64)
2
a, a† connect eigenstates of different quantum nos. n, as
(a†)n
|ni = |0i, (65)
(n!)1/2
where |0i is state which obeys a|0i = 0. Operating on |ni with a† may
be shown with use of commutation relations to give
a†|ni = (n + 1/2)1/2|n + 1i ; a|ni = n1/2|n − 1i (66)
so with these defs. the ladder operators for SHO are seen to be identical
to boson creation and annihilation operators defined above in Sec. 1.3.2.

1.4.2 1D harmonic chain

If we now consider N atoms on a linear chain, each attached to its neighbor
with a “spring” of spring constant K as shown in figure. First let’s consider
the problem classically. The Hamiltonian is
X p2` K
H= + (q` − q`+1)2, (67)
` 2m 2
18
where the q`’s are the displacements from atomic equilibrium positions.
Now Hamilton’s eqns. (or Newton’s 2nd law!) yield
−M q̈j = M ω 2 qj = K(2qj − qj−1 − qj+1). (68)
A standing sinusoidal wave qj = A cos(kaj) satisfies this equation if the
eigenfrequencies have the form
K
ωk2 = 2(1 − cos ka), (69)
M
where if a is the lattice constant, k = 2π/λ. Note that for small k, ωk is
linear, ωk ' (K/M )1/2ka.13
This is the classical calculation of the normal modes of oscillation on
a 1D chain. To quantize the theory, let’s impose canonical commutation
relations on the position and momentum of the `th and jth atoms:
[q`, pj ] = ih̄δ`m (70)
and construct collective variables which describe the modes themselves
(recall k is wave vector, ` is position) :
1 X ika` 1 X −ika`
q` = e Q k ; Qk = e q`
N 1/2 k N 1/2 `
1 X −ika` 1 X ika`
p` = e p k ; P k = e p` , (71)
N 1/2 k N 1/2 `
which leads to canonical commutation relations in wave vector space:
1 X −ikal ik0am
[Qk , Pk0 ] = e e [q`, pm]
N `,m
ih̄ X −ial(k−k0 )
= e = ih̄δk,k0 . (72)
N `
Let’s now express the Hamiltonian (67) in terms of the new variables. We
have, with a little algebra and Eq. (69),
X X
p2` = Pk P−k (73)
` k
K X K X M X
(q` − q`−1)2 = Qk Q−k (2 − eika − e−ika ) = ωk2 Qk Q−k
2 ` 2 k 2 k
13
Note since k = 2πn/(N a), the ωk are independent of system size

19
 so
1 X MX 2
H= pk p−k + ω Qk Q−k . (74)
2M k 2 k k
Note that the energy is now expressed as the sum of kinetic + potential
energy of each mode k, and there is no more explicit reference to the
motion of the atomic constituents. To second quantize the system, we
write down creation and annihilation operators for each mode k. Define
   

M ωk 1/2  i
ak = Qk + P−k  (75)
2h̄ M ωk
 1/2  
M ω i
a†k = 
k
−k −
Q Pk  (76)
2h̄ M ωk
which can be shown, just as in the single SHO case, to obey commutation
relations
 
ak , a†k0 = δkk0 (77)
[ak , ak0 ] = 0 (78)
 
† †
ak , ak 0 = 0 (79)
and the Hamiltonian expressed simply as
 
X 1
h̄ωk a†k ak
+  (80)
k 2
which we could have probably guessed if we had realized that since the
normal modes don’t interact, we have simply the energy of all allowed
harmonic oscillators. Note this is a quantum Hamiltonian, but the energy
scale in H is the classical mode frequency ωk .

1.4.3 Debye Model

Let us imagine using the Hamiltonian (80) as a starting point to calculate
the specific heat of a (3D) solid due to phonons. We take the Debye model
for the dispersion to simplify the calculation,


 ck k < kD
ωk =   0
(81)
k > kD
20
where the Debye wave vector kD = (6π 2n)1/3 is obtained by replacing the
first Brillouin zone of the solid by a sphere of radius kD which contains
N wave vectors, with N the number of ions in the crystal. The average
value of the Hamiltonian is
   
X † 1 X 1 1
U = hHi = 3 h̄ωk hak ak i +  = 3 h̄ωk  βh̄ω +  (82)
k 2 k e k−1 2
since the average number of phonons in state k is simply the expectation
value of a boson number operator
ha†k ak i ≡ Tr(ρa†k ak ) = b(h̄ωk ), (83)
where b(x) = (exp(βx) − 1)−1 is the free Bose distribution function. The
factors of 3 come from the 3 independent phonon polarizations, which we
consider to be degenerate here. Taking one derivative wrt temperature,
the spec. heat per unit volume is
∂u ∂ X h̄ck ∂ h̄c Z kD k3
cV = =3 =3 dk βh̄ck
∂T n ∂T k eβh̄ck − 1 ∂T 2π 2 0 e −1
 
∂ 3(kB T )4 Z ∞ x3 ∂ π 2 (kB T )4 2π 2  kB T 3
' = = kb (84)
∂T 2π 2(h̄c)3 | 0 e{zx − 1} ∂T 10 (h̄c)3 5 h̄c
π 4/15

So far we have done nothing which couldn’t have been done easily by or-
dinary 1st-quantized methods. I have reviewed some Solid State I material
here by way of introduction to problems of interacting particles to which
you have not been seriously exposed thus far in the condensed matter grad
sequence. The second quantization method becomes manifestly useful for
the analysis of interacting systems. I will now sketch the formulation (not
the solution) of the problem in the case of the phonon-phonon interaction
in the anharmonic crystal.

21
1.4.4 Anharmonicity & its consequences
As you will recall from Solid State I, most thermodynamic properties of
insulators, as well as neutron scattering experiments on most materials,
can be explained entirely in terms of the harmonic approximation for the
ions in the crystal, i.e. by assuming a Hamiltonian of the form (80). There
are some problems with the harmonic theory. First, at higher tempera-
tures atoms tend to explore the anharmonic parts of the crystal potential
more and more, so deviations from predictions of the equilibrium theory
increase. The thermal expansion of solids in the harmonic approxima-
tion is rigorously zero.14 Secondly, some important qualitative aspects of
transport cannot be understood: for example, the harmonic theory pre-
dicts infinite thermal transport of insulators! (See A&M Ch. 25 for a
qualitative discussion of these failures).
The obvious way to go beyond the harmonic approximation is to take
into account higher-order corrections to the real-space crystal potential
systematically, expanding15
1 X (2) 1 X (3)
U= D (`, m)q`qm + D (`, m, n)q`qm qn + . . . , (86)
2! `m 3! `mn
where
(n) ∂ nU
D (`, m, . . . n) = (87)
∂q`∂qm . . . ∂qn ui=0
14
This follows from the independence of the phonon energies in harmonic approx. of the system volume. (see
above) Since pressure depends on temperature only through the volume derivative of the mode freqs. (see A & M p.
490),  
  ∂p
∂V ∂T
=  V = 0 (85)
∂T p ∂p
∂V
T

15
I have dropped polarization indices everywhere in this discussion, so one must be careful to go back and put
them in for a 2- or 3D crystal.

22
are the so-called dynamical matrices.16 Using Eqs. (71,76) we find
 
1  h̄ 1/2 X X
q` = √ Qk eika` = (ak + a†−k )eika` (88)
N 2mω k k

Note that the product of 3 displacements can be written

1 X
q`qm qn = 3/2
ei(k1 a`+k2am+k3 an)Qk1 Qk2 Qk3 (89)
(N ) k1k2 k3
so the cubic term may be written
X
H3 = V (3)(k1k2k3)Qk1 Qk2 Qk3 (90)
k1 k2 k3

with
X
V (3)(k1k2k3) = D (3)(`, m, n) exp[i(k1` + k2m + k3n)] (91)
`mn

Note now that the indices `, m, n run over all unit cells of the crystal
lattice. Since crystal potential itself is periodic, the momenta k1, k2, and
k3 in the sum are not really independent. In fact, if we shift all the sums
in (91) by a lattice vector j, we would have

X
V (3)(k1k2k3) = D (3)(` + j, m + j, n + j)ei(k1 a`+k2 am+k3an) ei(k1 +k2+k3)aj
`mn
X
= D (3)(`, m, n)ei(k1a`+k2 am+k3an) ei(k1 +k2+k3)aj (92)
`mn

where in the last step I used the fact that the crystal potential U in every
lattice cell is equivalent. Now sum both sides over j and divide by N to
find
X
V (3)(k1k2k3) = D (3)(`, m, n) exp[i(k1` + k2m + k3n)]∆(k1 + k2 + k3),
`mn
(93)
16
Recall that the theory with only harmonic and cubic terms is actually formally unstable, since arbitrarily large
displacements can lower the energy by an arbitrary amount. If the cubic terms are treated perturbatively, sensible
answers normally result. It is usually better to include quartic terms as shown in figure below, however.

23
where
1 X i(k1 +k2+k3)aj 1 X
e
∆(k) = = δ(k + G) (94)
N j N k
and G is any reciprocal lattice vector.
Return now to (90). We have ascertained that V (3)(`, m, n) is zero
unless k1 + k2 + k3 = G, i.e. crystal momentum is conserved. If we
expand (90), we will get products of 3 creation or annihilation operators
with coefficients V (3). The values of these coefficients depend on the elastic
properties of the solid, and are unimportant for us here. The momenta
of the three operators must be such that momentum is conserved up to a
reciprocal lattice vector, e.g. if we consider the term ak1 a†−k2 a†−k3 we have
a contribution only from k1 + k2 + k3 = G.17 Note this term should be
thought of as corresponding to a physical process wherein a phonon with
momentum k1 is destroyed and two phonons with momenta −k2 and −k3
are created. It can be drawn ”diagrammatically” à la Feynman (as the
1st of 2 3rd-order processes in the figure below).
p
k
k
q

q
p k q

k k
p q'
p
p
q' q'
q q

Figure 4: Diagrams representing phonon-phonon collision processes allowed by energy and momen-
tum conservation in 3rd and 4th order.

17
As usual, processes with G = 0 are called normal processes, and those with finite G are called Umklapp processes.

24
Questions:

• How does energy conservation enter? What is importance of processes

involving destruction or creation of 3 phonons?
• If one does perturbation theory around harmonic solution, does cubic
term contribute to thermal averages?
• Can we calculate thermal expansion with cubic Hamiltonian?

25