“A theory is the more impressive the greater the simplicity

of its premises, the more different kinds of things it relates

and the more extended is its area of applicability.”

A. Einstein, Autobiographical notes, Library of Living

Philosophers, Evanston, IL (1949).

Chapter 9

The 2-Level System

9.1 Schottky Heat Capacity

When insulators or semiconductors contain impurities with closely spaced electronic
or nuclear ground states1 heat capacities CV show an anomalous low temperature
peak, the so called “Schottky anomaly.”2 This is an example of how microscopic
quantum effects generate macroscopic (thermodynamic) signatures.

9.1.1 Schottky Model

A simple model for “Schottky” behavior consists of a crystal containing a dilute3

concentration of N identical atomic impurities, each having the same pair of closely
spaced, non-degenerate energy levels – a lower state 1 and a higher state 2 . If at
some temperature T , n1 impurity atoms are in the low energy state and n2 are in
the higher energy state the system eigen-energies are

E (n1 , n2 ) = n1 1 + n2 2 (9.1)
1
Usually degenerate low energy states whose degeneracy is lifted by crystalline electric fields,
magnetic fields, spin-orbit coupling or hyperfine interactions.
2
The phenomenon is named for Walter Hermann Schottky (1886-1976).
3
Diluteness insures negligible inter-atomic effects.

1
2 CHAPTER 9. THE 2-LEVEL SYSTEM

with the “least bias” Lagrangian

N
L = −kB ∑ P (n1 , n2 ) ln P (n1 , n2 )
n1 ,n2
n1 +n2 =N
N N
(9.2)
−λ1 ∑ P (n1 , n2 ) (n1 1 + n2 2 ) − λ0 ∑ P (n1 , n2 ) ,
n1 ,n2 n1 ,n2
n1 +n2 =N n1 +n2 =N

where P (n1 , n2 ) is the probability that n1 impurity atoms are in the state 1 and
n2 are in the state 2 . The method of Lagrange multipliers gives the “least bias”
probabilities

e−β(n1 1 +n2 2 )
P (n1 , n2 ) = (9.3)
Z

where again λ1 = T1 .4 With β = 1 the partition function is

kB T
N
Z= ∑ e−β(n1 1 +n2 2 ) . (9.4)
n1 ,n2
n1 +n2 =N

One way to express the sum over all states is by explicitly including the configura-
tional degeneracy [see Chapter 5]

N!
g(n1 , n2 ) = (9.5)
n1 ! n2 !
to give
N
N ! −β(n1 1 +n2 2 )
Z= ∑ e (9.6)
n1 ,n2 n1 ! n2 !
n1 +n2 =N

which is the binomial expansion of

N
= (e−β1 + e−β2 ) . (9.7)

Immediately from Eq.9.7 we find the thermodynamic properties:

4
The reason, of course, is that temperature T is the state variable conjugate to Entropy, i.e. T S
is a natural conjugate pair. [See Eq.??.]
9.1. SCHOTTKY HEAT CAPACITY 3

A. Internal energy:

∂
U =− ln Z (9.8)
∂β
1 e−β1 + 2 e−β2
=N −β1 (9.9)
e + e−β2

B. Entropy:

S = − kB ∑ P (n1 , n2 ) ln P (n1 , n2 ) (9.10)

n
∂ 1
= − kB β 2 ( ln Z) (9.11)
∂β β
(1 e−β1 + 2 e−β2 )
=N kB [ln (e−β1 + e−β2 ) + β ] (9.12)
(e−β1 + e−β2 )

C. Heat capacity: In laboratory measurements the external thermodynamic

constraint on solids is usually constant pressure (atmospheric pressure). A
measured heat capacity is then Cp . However microscopic models naturally
produce CV , i.e.
∂S
CV = T ( ) (9.13)
∂T V
or, equivalently, for a system of fixed density ρ, N = ρV
∂S
CN = T ( ) . (9.14)
∂T N
For simplicity taking 1 = 0, 2 − 1 = ∆ and using Eq.9.12 and 9.14
2 eβ∆
CN = N kB (β∆) 2 (9.15)
(eβ∆ + 1)
or in terms of a dimensionless plotting coordinate X = β ∆
CN eX
= X2 2 . (9.16)
N kB (eX + 1)
4 CHAPTER 9. THE 2-LEVEL SYSTEM

Figure 9.1: Schottky heat capacity anomaly. The abscissa is taken to be X −1 = k∆
BT

to emphasize the characteristic low temperature Schottky peak.

Plotting this in Figure 9.1 a Schottky peak appears at X −1 = k∆

B T = 0.417.

Although the low temperature heat capacity of insulating crystals has a

dominant ∼ T 3 contribution from lattice vibrations, the sharp Shottky peak
can usually be distinguished above this lattice baseline.
In the high temperature limit, X << 1, Eq.9.16 reduces to
CN X2
→ (9.17)
N kB 4
∆ 2
=( ) . (9.18)
2kB T

At low temperature, X >> 1, Eq.9.16 becomes

CN
→ X 2 e−X (9.19)
N kB
∆ 2 − k∆T
=( ) e B (9.20)
kB T

which has the limiting behavior

lim CN = 0 . (9.21)
T →0
9.1. SCHOTTKY HEAT CAPACITY 5

9.1.2 Two Level Systems and Negative Temperature

Writing Eq.9.9 as

1
U = N ∆ (9.22)
1 + eβ∆
and Eq.9.12 as

β∆
S = N kB [ln (1 + e−β∆ ) + ], (9.23)
eβ∆+1

a dimensionless internal energy can be defined, Φ = NU∆ . Then entropy can be

written in terms of Φ as
S
= (Φ − 1) ln (1 − Φ) − Φ ln Φ . (9.24)
N kB

which is plotted in Figure 9.2.

Figure 9.2: S vs.Φ. The region 0.5 < Φ ≤ 1 corresponds to negative temperature.
6 CHAPTER 9. THE 2-LEVEL SYSTEM

Now, from the “thermodynamic identity” written as

T dS = N ∆ dΦ + pdV (9.25)

or
N ∆ p
dS = dΦ + dV , (9.26)
T T
the slope [See Figure 9.2]

1 ∂S ∆ε
( ) = (9.27)
N ∂Φ N T
is:
a. Positive (temperature is positive) for Φ < 0.5
b. Zero (temperature is infinite) at Φ = 0.5
c. Negative (temperature is negative) for Φ > 0.5
To achieve negative temperatures the internal energy of the system must have an
upper bound, a condition satisfied by the two level Schottky system. Negative tem-
perature means that a population of excited atoms is unstably inverted, i.e. the
system is not in a state of thermodynamic equilibrium and is, at the slightest trig-
ger, ready to dump its excess energy into the ground state. In this sense negative
temperatures are “hotter” than positive temperatures.
Since the two level system is never really isolated – i.e. phonons, radiation, magnetic
excitations, etc. are usually available for interaction – it is rare to find a true nega-
tive temperature condition, except in idealized models. There are, however, special
circumstances in which strongly prohibitive selection rules prevent “triggers” from
acting except on long time scales. Population inversion in lasers is one example in
which a negative temperature is maintained until a photon is allowed to “stimulate”
the inverted population into a downward avalanche.