Micro and Macrostates

Welcome back
to PHY 3305
Today’s Lecture:
Statistical Mechanics
Satyendra Nath Bose

1894 - 1974
Physics 3305 - Modern Physics Professor Jodi Cooley
Wednesday, April 11, 2012

Announcements
• Chapter 9 reading assignment:
Appendix J, 9.1 - 9.9
• Problem Set 10 is due Tuesday, April 17th.
• Tuesday, April 10th - initial outline of topic with
primary points
• Monday, April 16th - Office Hours Cancelled
• Tuesday, April 17th - complete draft of talk
• Week of April 24th - final presentations

Review: Statistics
If we have N things that can be arranged into M groups -
N! W = number of ways of
W = !M
i=1 Ni ! arranging things
A typical case is M = 2 -- a two state system where we

define the number of objects in one state as n and in the
other state as N - n
N!
W = Binomial Coefficient
n!(N − n)!
! "
N
Short hand notation: W =
n

Review: Micro- & Macro- States
Microstates
The microstate is the state of the system given
complete microscopic knowledge.
Macrostate:
The macrostate describes an overall condition of being,
achieved by many possible microstates.
- to know the macrostate is to know properties that

don’t depend on the exact microscopic states of
individual particles

Review Question 1
A collection of three particles shares 3 units of energy.
Each particle is restricted to having an integral number
of units of energy. How many macrostates are there?
Answer: 3
State A in which 1 particle has 3 units of energy and
the others have none.
State B in which 1 particle has 2 units of energy, one
particle has 1 unit of energy and the other none.
State C in which each particle has 1 unit of energy.

Review Question 2
A collection of three particles shares 3 units of energy.
Each particle is restricted to having an integral number
of units of energy. How many microstates are there in
each macrostate?
Answer:
Macrostate A has 3 micorstates: 300, 030, 003
Macrostate B has 6 micorstates: 210, 201, 021, 120,
012, 102
Macrostate C has 1 microstate: 111

Consider a large number of distinguishable particles
in equilibrium. How is the energy distributed among
the particles in the system when it is in equilibrium?
What might we need to take into consideration?
- Each particle is in a given state of energy. So, we

will need to know how many are in a given state.
- Energy is constantly being exchanged randomly
between the particles.
We can use probabilities to simply the problem.

What do we need to know to compute the probability
of finding a particle in a given energy state?
In general:
In our case, we are looking for the probability that

particle i will possess energy Eni -- it’s quantum number
will be ni:

Case: Harmonic Oscillator
Consider a system of N
identical but distinguishable
harmonic oscillators which
are exchanging energy in
some unspecified way
(one oscillator jumps to a higher
energy as another drops to a lower energy).
Note: The energy of a harmonic oscillator depends only
on a single quantum number.
Simplify by shifting the potential energy by

which makes the ground state energy 0.

The energy of the ith oscillator in the nith energy level is
then
The total energy of N oscillators is
where
Note: M (sum of all quantum
numbers) is directly proportional
to the total energy.

The number of ways N integers (the particle’s quantum
numbers) can be added to give the integer M is given by
Recall
We need this! We just found this!
The number of ways energy can be distributed with ni fixed

is the the number of ways the N-1 other quantum numbers
can be added to give M-ni.

Putting it together, we have
Let’s put in some numbers. Say we have 10 oscillators and

the sum of their quantum numbers is 50.
What is the average energy per particle?
E M h̄ω0 50h̄ω0
Ē = = = = 5h̄ω0
N N 10
The average oscillator occupies its 5th energy level.

Calculate the probability that particle/oscillator i has the
average energy, ni = 5.
53!
45!(53−45)! 8.86 × 108
Pni =5 = 59! =
50!(59−50)! 1.26 × 1010
Pni=5 = 0.0705

Probabilities of a given
oscillator being in its ni state.
In a system of particles, varying the energy of just one particle

causes sharp changes in the way energy is then distributed amongst
all the other particles.
The greatest freedom to distribute energy amongst particles occurs
when that one particle has the least energy possible.
Thus, the most probable state particles for a given particle is the
one of lower energy.

The equation we used is for a special case, harmonic
oscillator, and it is very cumbersome to use.
In the limit of large systems of distinguishable particles, it

can be shown that ALL cases converge to the Boltzman
probablity.
Probability that in a large system of temperature T, an

individual particle will be in state n of energy En. (Note:
here n stands for all quantum numbers - n, l, ml, ms needed
to specify the individual-particle state.)

Matches our exact probabilities!

We have
Boltzmann Probability
How might we determine the factor A?

We need to normalize the probability.
!
P (En ) = 1
n
Note: Error in A 1
on page 359 of A= ! −En
e kB T
your textbook.
n

Thus, the Boltzmann probability is
How do we compute the average of a wave function?

Answer: We compute it’s expectation value.
We can do the same here to compute the average
energy of a system.

What does that give us for a system of harmonic oscillators?
Recall, we had shifted the potential energy so that we
could write
Substituting we find
Simplification is left as an exercise for the student.


Average Energy of a
system of harmonic
oscillators.
Note: This result

provides a link between
temperature, energy
and probability.
E M h̄ω0
Ē = =
N N

Occupation Number
Occupation Number: how many particles are in a state
of Energy En.
Here again n refers to
all quantum numbers.
Note: This is not the same as “the number of particles

with an energy, En” - it is possible that several states may
have the same energy.
If En = En! ≡ E
then you have to add occupation numbers of those
states together to get the “number of particles of
energy E”.

This means
We can rewrite the average energy in terms of occupation

number (for convenience).

Example: Hydrogen Atoms
Consider a sample of hydrogen atoms at a room
temperature of 300 K. What is the ratio of the
number of atoms in the n = 2 energy levels to those in
n = 1? Although ordinary hydrogen exists as a diatomic
gas, consider individual atoms to simplify this problem.

Recall that when two different wave functions have
the same energy, it is called a degeneracy. Hydrogen’s
degeneracy is 2n2.
n2 -> due to different l and ml values (pg 258)

2 -> due to the lone electron’s two allowed
values of ms.

What is then the degeneracy of the n = 2 level?
Answer = (2 x 22) = 8
What is then the degeneracy of the n = 1 level?
Answer = (2 x 12) = 2
Aside 1: Identify the energy states {n, l, ml, ms} have the
same energy E2 and E1?
E2: {2, 0, 0, -1/2} E1: {1, 0, 0, 1/2}
{2, 0, 0, 1/2} {1, 0, 0, -1/2}
{2, 1, 1, 1/2}
{2, 1, 1, -1/2}
{2, 1, -1, 1/2}
{2, 1, -1, -1/2}
{2, 1, 0, 1/2}
{2, 1, 0, -1/2}

The ratio of the number of atoms with energy E2
to atoms with energy E1 is then given by
Now we recall that

−13.6
En =
n2

So the energy difference is
A calculation of the quantity kBT yields
How do we convert between J and eV?
1 eV = 1.6 x 10-19 J

Putting it all together.
What does this mean?
At room temperature there is almost no chance of

finding a hydrogen atom in an excited state.

At what temperature would the ratio of molecules in
the n = 2 energy levels to those in the n = 1 energy
levels be 1/10?
From our previous calculation, we know
Note: Tsun ~ 6000 K

From Sums to Integrals
In classical physics the discrete quantum levels are closely
spaced and we can replace the sums with which we have
been dealing with integrals.
Can we do this with quantum mechanics?
Answer: Yes, if the quantum levels are closely

spaced.
What do I mean by closely spaced?

As an illustration, let’s examine an example.

Consider the ratio of the Boltzmann probability at energy
En to its value at the next higher energy level En+1.
If En+1 - En is much smaller than kBT, than the ratio

equals 1 and the energy levels are considered closely
spaced.
What should we integrate over?
Energy is varying slowly

over n. So, in theory dn.
This is not so convenient.

Energy may be an alternative. However, we must be
cautious. Consider the case of energy in a collection
of hydrogen atoms.
Examine the numerator -
Since energy depends only on quantum number, n, this sum

over states can be written as a sum over energies E1 & E2.

So, now we have
In order to change to an integral, we should replace

discrete En by a continuous variable E. However, we still
need to include the number of states at the given
energy.

If E becomes continuous, the number of states at a
particular energy becomes differentially small and we can
account for this through the number of states per range of
energy.
This quantity is known as the density of states, D(E).

Applying this to our equation for average energy, we
have an expression for the limit of closely spaced
energy levels.

The end
(for today)

Micro and Macrostates

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Welcome back

Satyendra Nath Bose

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

A typical case is M = 2 -- a two state system where we

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

- to know the macrostate is to know properties that

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

- Each particle is in a given state of energy. So, we

We can use probabilities to simply the problem.

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

In our case, we are looking for the probability that

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

Simplify by shifting the potential energy by

Wednesday, April 11, 2012

The total energy of N oscillators is

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

We need this! We just found this!

The number of ways energy can be distributed with ni fixed

Wednesday, April 11, 2012

Let’s put in some numbers. Say we have 10 oscillators and

What is the average energy per particle?

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

In a system of particles, varying the energy of just one particle

Wednesday, April 11, 2012

In the limit of large systems of distinguishable particles, it

Probability that in a large system of temperature T, an

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

How might we determine the factor A?

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

How do we compute the average of a wave function?

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

Simplification is left as an exercise for the student.

Wednesday, April 11, 2012

Note: This result

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

Note: This is not the same as “the number of particles

Wednesday, April 11, 2012

We can rewrite the average energy in terms of occupation

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012

Physics 3305 - Modern Physics Professor Jodi Cooley

Wednesday, April 11, 2012