Lecture Supplement

The Einstein Model of a Solid

Our objective is to articulate the Einstein model of a solid, a certain
simple microscopic model, and to show how statistical mechanics can be
used to determine the thermodynamics of an Einstein solid.
A real solid is composed of atoms that are joined by bonds electromagnetic interactions between the atoms. We can think of these bonds as
springs connecting the atoms. If the springs that model the bonds are taken
to be Hookes Law springs, then we obtain a model called the Debye Model
of a solid. In this model, when one heats up a solid, the atoms begin to jiggle
around. The heat that is transferred to the solid is stored in the kinetic
energy of the motion of the atoms as they jiggle and in the potential energy
of the springs as they stretch or compress.
A simpler model of a solid that turns out to work at high temperatures is a
model in which atoms are assumed to be weakly-coupled. This means that
each atom is considered to have a certain energy depending on how much its
jiggling, and atoms can share energy between one another, but the energy
stored in the interactions between the atoms is ignored. Mathematically,
this means that we model each atom as a harmonic oscillator that can have
a certain energy, and atoms can share energy with one another, but the total
energy of the whole solid is just the sum of the energies of the individual
oscillators there are no terms in the total energy corresponding to the
energy stored in the interaction between oscillators.
The Einstein model is a quantum model. This means that each atom is
modeled as a quantum harmonic oscillator. In particular, this implies that
each atom has a certain discrete set of possible energies called its energy
spectrum. These energies are sometimes labeled
0 , 1 , 2 , . . .

(1)

Each of these energies corresponds to a unique energy state, and in Dirac

notation these states are typically labeled as follows:
|0i , |1i , |2i , . . .

(2)

There is only one possible energy state corresponding to each possible energy value, and in quantum mechanics and linear algebra we would therefore
1

say that the energy spectrum of the quantum harmonic oscillator is nondegenerate. There are an infinite number of energies and corresponding
energy states, and the set of all possible states of the quantum harmonic
oscillator is spanned by the energy eigenstates.
In a quantum mechanics class, one derives a nice expression for the energies of a quantum harmonic oscillator:
n = (n + 12 )~

(3)

Where is the angular frequency of the given oscillator. Recall that the
angular frequency of a mass on a spring in classical mechanics is related to
the mass and the spring constant k of the spring by
r
k
(4)
=
m
In particular, the angular frequency is higher as the spring gets stiffer. This
intuition can still be instructive in the quantum case. Higher angular frequencies indicate that the quantum oscillator has a stiffer spring. An important
property to note about the energy spectrum of the quantum harmonic oscillator is that successive energy values in its spectrum have uniform separation:
n+1 n = ~.

(5)

If we call this separation, namely if we define

 = ~,

(6)

then an arbitrary energy value in the spectrum can be written as follows:

n = 12  + n.

(7)

Notice that the first term is just the energy of the ground state, the state
of lowest energy:
1

2

= 0 ,

(8)

So we can can write the energies of all state, including the excited states
having n 1, as
n = 0 + n.
2

(9)

The ground state energy is also often called the zero-point energy of the
quantum oscillator. In the Einstein model of a solid, we imagine that a solid
consists of N -independent quantum harmonic oscillators each with the same
energy spectrum characterized by the energy separation . The fact that
these oscillators are independent means, in particular, that the total energy
of the solid is the sum of the energies of the individual oscillators:
U = (0 + n1 ) + (0 + n2 ) + + (0 + nN )
| {z }
| {z }
| {z }
first oscillator

second oscillator

(10)

nth oscillator

= N  + (n1 + n2 + + nN )

(11)

In this notation ni denotes the energy state that the ith oscillator is occupying.
The term N  is the zero-point energy of the entire solid, which we will call
U0 .
U = U0 + (n1 + n2 + + nN ).

(12)

The term involving the sum of the ni s is the additional energy due to excitations of the solid. A microstate of the solid is an exact specification
of the sequence of ni s telling us precisely which energy state is occupied by
each oscillator. In dirac notation, such a state might be written in one of the
following equivalent ways:
|n1 , n2 , . . . , nN i ,

|n1 i |n2 i |nN i .

(13)

For example, if there are five oscillators, then a microstate of the system
could be


13, 0, 0, 2, 107 .
(14)
This is a state in which the first oscillator is in the thirteenth excited state, the
second and third oscillators are in their ground states, the fourth oscillator
is in its second excited state, and the fifth oscillator is in the ten-millionth
excited state. Notice that the total energy of the solid depends only on the
sum of all the ni s, not on the exact microstate of the system, so its useful
to have a label for this sum. Its common to use q for this label:
q = n1 + n2 + + nN .

(15)

This number represents the total number of energy units  are present in the
solid above its ground state. Notice that the total energy of the whole solid
is determined by q and N .
U = U0 + q.

(16)

We call a specification of the pair (q, N ) the macrostate of the solid. Notice
that since q uniquely determines U and vice versa, we could also specify the
its macrostate of the solid with the pair (U, N ). This is just like how we
would specify the macroscopic thermodynamic state of a sample of ideal gas
in a cylinder by a specification of the triple (U, V, N ). The volume of the
solid is ignored in the Einstein model even though the volume of a real solid
is important and can change due to changes in, say, temperature or pressure.

Thermal physics of an isolated Einstein solid

In order to predict the thermodynamic behaviors of the Einstein solid, we

need to determine an expression for the entropy of an Einstein solid in terms
of its energy and particle number. In other words, we need to determine an
expression for the entropy of an Einstein solid as a function of its macrostate.
For a solid with a fixed macrostate, namely for a solid with a particular
specification of the pair (U, N ), the entropy of the solid is proportional to
the natural logarithm of the number of microstates accessible to the system
given its macrostate:
S = kB ln .

(17)

The constant of proportionality is Boltzmanns constant. We therefore see

that in order to compute S(U, N ), we need to compute the number of accessible microstates as a function of a given macrostate (U, N ) or equivalently
(q, N ). Some combinatorics (see Schroeder pages 54-55) shows that


N +q1
(q, N ) =
.
(18)
q
Taking the natural log of this and multiplying by Boltzmanns constant therefore gives the desired entropy, and now we can, in principle, compute any
thermodynamic quantity whatsoever that we want for an Einstein solid (temperature, chemical potential, heat capacities, etc.)
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Temperature of the isolated Einstein solid

The temperature of the Einstein solid can be computed using the general
expression for temperature valid for any thermodynamic system. Recall that
the general expression is


S
1
=
.
(19)
kB T
U X1 ,...,Xn
For the Einstein solid, one has X1 = N , and there are no other parameters
necessary to specify the macroscopic state of the system, so the temperature
is


1
S
=
.
(20)
T
U N
Using the chain rule, we can compute the right-hand side as follows:
 
S
1
dq
=
T
q N dU

(21)

Since
1
q = (U U0 ),


(22)

1
dq
=
dU


(23)

we have

and therefore

=
T

S
q


(24)
N

Now we use the explicit expression for S(q, N ) derived in the last section


N +q1
S(q, N ) = kB ln (q, N ) = kB ln
(25)
q
This expression is only defined for integers N and q since the binomial coefficient is defined in terms of factorials, so we cant yet take the derivative
5

of this expression with respect to q to obtain the temperature. However,

its possible to extend the factorial to non-integer values using the gamma
function which is a smooth function with the property that
n! = (n + 1).

(26)

Once we do this, we see that

(N + q)
(q + 1)(N )
= kB [ln (N + q) ln (q + 1) ln (N )]

S(q, N ) = kB ln

(27)
(28)

To determine the temperature, we need to take the derivative of both sides

with respect to q. Noting that the derivative of the log of the gamma function
is the digamma function often denoted by a :
d
ln (x) = (x)
dx

(29)

= kB [(N + q) (q + 1)]

(30)

We have


S
q


N

and therefore the temperature satisfies


kB T

= (q + N ) (q + 1).

(31)

The thermodynamic limit

A macroscopic solid will have around an Avogadros number, of particles in

it, namely it will have
N 1024 .

(32)

Therefore, its well-motivated to try to see what the large-N behavior is of

thermodynamic quantities like temperature. In taking this large N limit,
called the thermodynamic limit, its convenient to define the certain variable that represents the energy per particle in the solid:
=
6

q
.
N

(33)

Then the temperature relationship from the last section can be written as
follows:

kB T

= (N + N ) (N + 1).

(34)

Now, we imagine taking N large while keeping fixed. This corresponds to

increasing the side of the solid while keeping the energy per particle fixed.
This corresponds to the physical operation of take the large N limit by combining a bunch of solids, all with the same energy per particle, to create a
macroscopically large solid. Now, it turns out that for large argument, the
digramma function has the same behavior as the natural log:
(x) ln(x),

x  1,

(35)

So if we take N sufficiently large, then

(N + N ) ln(N + N )
(N + 1) ln(N + 1) ln(N ),

(36)
(37)

and our expression for the temperature becomes


kB T


ln(N + N ) ln(N ) = ln

+1


(38)

This shows that in the thermodynamic limit, the temperature is determined

entirely by the energy per particle, and has no dependence on the particle number. In particular, the temperature is an intensive quantity in the
thermodynamic limit (as we would expect!)