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Statistical Mechanics: Course Code - PPHY 302

1. The document discusses statistical mechanics and the concept of ensembles. An ensemble is a collection of hypothetical identical systems that represent all the possible microstates of a given macrostate. 2. Key terminology is introduced, including microstates and macrostates. Disorder is used synonymously with entropy. Examples are given where increasing disorder, like expanding an ideal gas, leads to higher entropy through increased freedom of movement. 3. The behavior of a two-state system is analyzed as it relates to internal energy, entropy, and heat capacity variations with temperature. There is a Schottky anomaly where heat capacity peaks at an intermediate temperature when transitions between the two states are most probable.

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50 views21 pages

Statistical Mechanics: Course Code - PPHY 302

1. The document discusses statistical mechanics and the concept of ensembles. An ensemble is a collection of hypothetical identical systems that represent all the possible microstates of a given macrostate. 2. Key terminology is introduced, including microstates and macrostates. Disorder is used synonymously with entropy. Examples are given where increasing disorder, like expanding an ideal gas, leads to higher entropy through increased freedom of movement. 3. The behavior of a two-state system is analyzed as it relates to internal energy, entropy, and heat capacity variations with temperature. There is a Schottky anomaly where heat capacity peaks at an intermediate temperature when transitions between the two states are most probable.

Uploaded by

Siva Arun
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Aum Sri Sai Ram

Statistical Mechanics
Course Code - PPHY 302
Lecture - 5
Recap on “ensembles”

2
Illustration of microstates (2 particles in a box)

3
Some terminology
Ensemble

For a given macrostate (N,V,E), a statistical system, at any time t, is


equally likely to be in any one of an extremely large number of distinct
microstates.

As time passes, the system continually switches from one microstate to


another.

Over a reasonable span of time, all one observes is a behavior “averaged”


over the variety of microstates through which the system passes.

4
Ensemble
It may, therefore, make sense if we consider, at a single
instant of time, a rather large number of systems — all being
some sort of “mental copies” of the given system — which are
characterized by the same macrostate as the original
system but are in all sorts of possible microstates.

This collection of systems is called an ensemble.

It is a mental construct.

5
6
Query on Entropy

Disorder is used as a synonym for entropy

7
Few examples

8
9
Expansion of an ideal gas
● The difference between the initial
state and the final state of the ideal
gas is an increase of volume,
which provides the gas particles
with more space for their motion.
● Disorder, in this case, is not linked
to a structural change that
provides freedom of movement, as
in the case of sublimation, but,
rather, more freedom of movement
is provided in a larger volume.
10
Ferromagnet and paramagnet
Ferromagnet

Paramagnet

In the microscopic picture, the magnetic moments of the ferromagnetic


material are mostly aligned in one direction (ordered). At temperatures
above the Curie point, the magnetic moments are randomly oriented
(disordered) to produce paramagnetic behavior. From a thermodynamic
point of view, the entropy increases in the transition from ferromagnetism
to paramagnetism. 11
Problem
Two-state system

12
13
14
Internal energy as a function of T

At low temperature, the


system is in the lower level
and the internal energy is
U = - Δ/2 .

At high temperature, the


two levels are each
occupied with probability
1/2, U therefore tends to 0
(which is halfway between
-Δ/2 and Δ/2)
15
Entropy as a function of T
At low temperature, the
system is in the lower level.

No. of microstates = 1

At high temperature, the two


levels are each occupied
with probability 1/2,
No. of microstates = 2
entropy tends to
16
Entropy as a function of T
The entropy rises as the
temperature increases because it
reflects the freedom of the system
to exist in different states, and at
high temperature the system has
more freedom (in that it can exist in
either of the two states).

Conversely, cooling corresponds to


a kind of “ordering” in which the
system can only exist in one state
(the lower), and this gives rise to a
reduction in the entropy.

17
Heat capacity as a function of T

The heat capacity is very small both


(i) at low temperature (kBT<<Δ) and
(ii) at very high temperature
(kBT>>Δ),

because changes in temperature


have no effect on the internal energy
when (i) the temperature is so low
that only the lower level is occupied
and even a small change in
temperature won’t alter that, and

(ii) the temperature is so


high that both levels are occupied
equally and a small change in
temperature won’t alter this.
18
Heat capacity as a function of T

At very low temperature, it is hard to


change the energy of the system
because there is not enough energy
to excite transitions from the ground
state and therefore the system is
“stuck”.

At very high temperature, it is hard to


change the energy of the system
because both states are equally
occupied.

19
Heat capacity as a function of T
In between, roughly around a

temperature T ≈ Δ/kB, the heat

capacity rises to a maximum,

known as a Schottky anomaly.

This arises because at this temperature, it is possible to thermally excite


transitions between the two states of the system.
20
Schottky anomaly

The Schottky anomaly is an effect observed in solid-state physics where


the specific heat capacity of a solid at low temperature has a peak. It is
called anomalous because the heat capacity usually increases with
temperature, or stays constant.

It occurs in systems with a limited number of energy levels

21

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