STATISTICAL

MECHANICS
BASIC METHODS
Dr. Syahida Suhaimi
Applied Physics, FST USIM 1
 Statistical Mechanics

a branch of theoretical
physics and chemistry (and mathematical physics)
that studies, using probability theory, the average
behaviour of a mechanical system where the state
of the system is uncertain.

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A common use of statistical mechanics is in
explaining the thermodynamic behaviour of large
systems.

Microscopic mechanical laws do not contain concepts

such as temperature, heat, or entropy,

however, statistical mechanics shows how these

concepts arise from the natural uncertainty that arises
about the state of a system when that system is
prepared in practice. 3
The benefit of using statistical mechanics
is that it provides exact methods to
connect thermodynamic quantities (such
as heat capacity) to microscopic
behaviour,
whereas in classical thermodynamics the
only available option would be to just
measure and tabulate such quantities for
various materials.
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Statistical mechanics also makes it possible
to extend the laws of thermodynamics to cases
which are not considered in classical
thermodynamics,

for example microscopic systems and other

mechanical systems with few degrees of freedom.

This branch of statistical mechanics which treats

and extends classical thermodynamics is known
as statistical thermodynamics or equilibrium
statistical mechanics.
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ENSEMBLE : Synonyms
1. totality, entirety, aggregate
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ahn-sahm-buh l,
THERE ARE 3 TYPES OF
ENSEMBLES:
• MICROCANONICAL
• CANONICAL
• GRAND CANONICAL

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• In statistical mechanics, a microcanonical ensemble is the statistical
ensemble that is used to represent the possible states of a
mechanical system which has an exactly specified total energy.

• The system is assumed to be isolated in the sense that the system

cannot exchange energy or particles with its environment, so that
(by conservation of energy) the energy of the system remains
exactly known as time goes on.

• The system's energy, composition, volume, and shape are kept the
same in all possible states of the system.

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• The macroscopic variables of the microcanonical ensemble are
quantities such as
(i)the total number of particles in the system (symbol: N),
(ii) the system's volume (symbol: V) each which influence the nature
of the system's internal states,
(iii) as well as the total energy in the system (symbol: E).

• This ensemble is therefore sometimes called the NVE ensemble, as

each of these three quantities is a constant of the ensemble.

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• In simple terms, the microcanonical ensemble is defined by
assigning an equal probability to every microstate whose energy
falls within a range centered at E. All other microstates are given a
probability of zero. Since the probabilities must add up to 1, the
probability P is the inverse of the number of microstates within
the range of energy,

P= 1/
• The range of energy is then reduced in width until it
is infinitesimally narrow, still centered at E. In the limit of this
process, the microcanonical ensemble is obtained.

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2. CANONICAL ENSEMBLE:

The system is in thermal equilibrium with a

heat reservoir at temperature T.

Hence the temperature of the system is

constant; but the energy of the system is not
constant.

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• In statistical mechanics, a canonical
ensemble is the statistical ensemble that is
used to represent the possible states of a
mechanical system which is in thermal
equilibrium with a heat bath.
• The system is said to be closed in the sense
that the system can exchange energy with a
heat bath, so that various possible states of
the system can differ in total energy. The
system's composition, volume, and shape are
kept the same in all possible states of the 14
system.
• The thermodynamic variable of the canonical
ensemble is the absolute temperature (symbol: T).
• The ensemble is also dependent on mechanical
variables such as
(i)the number of particles in the system (symbol: N)
(ii)the system's volume (symbol: V), each which
influence the nature of the system's internal states.
This ensemble is therefore sometimes called
the NVT ensemble, as each of these three quantities
is a constant of the ensemble.
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• In simple terms, the canonical ensemble assigns a
probability P to each distinct microstate given by the
following exponential:

• where E is the total energy of the microstate,

and k is Boltzmann's constant.

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• The number A is the free energy (specifically, the
Helmholtz free energy) and is a constant for the ensemble.
• However, the probabilities and A will vary if different N, V, T are
selected.
• The free energy A serves two roles: to provide a normalization
factor for the probability distribution (the probabilities, over the
complete set of microstates, must add up to one); and, many
important ensemble averages can be directly calculated from the
function A(N, V, T).

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3. GRAND CANONICAL ENSEMBLE:
The system is in contact with both a heat reservoir
and a particle reservoir.

(i) the U and N of the system are not

constant.
(ii) the T and the  are constant.

(the is the energy required to add a particle to

the system)
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• In statistical mechanics, a grand canonical ensemble is
the statistical ensemble that is used to represent the possible states
of a mechanical system of particles that is being maintained
in thermodynamic equilibrium (thermal and chemical) with a
reservoir.

• The system is said to be open in the sense that the system can
exchange energy and particles with a reservoir, so that various
possible states of the system can differ in both their total energy
and total number of particles. The system's volume, shape, and
other external coordinates are kept the same in all possible states
of the system.

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• The thermodynamic variables of the grand canonical ensemble
are chemical potential (symbol: µ) and absolute
temperature (symbol: T).

• The ensemble is also dependent on mechanical variables such as

volume (symbol: V) which influence the nature of the system's
internal states.

• This ensemble is therefore sometimes called the µVT ensemble, as

each of these three quantities are constants of the ensemble.

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 SUMMARY

NVE ensemble NVT ensemble µVT ensemble

U constant; U not constant; T ,  constant;

N, V, E T constant; U, N not constant;
constant; In contact with In contact with Heat and
Isolated system Heat reservoir Particle reservoir 22
Closed system Open system
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Consider TWO cases:

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Ui : ground state
Uj: excited state
& Pi: probability in the ground state i
Pj: probability in the excited state j
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Application of classical statistics

Example 1: At room temperature, what would be the ratio of hydrogen

atoms in the first excited state to the number in the ground state?
Ignore degeneracies.

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(k = 8.63 x 10-5 eV/K ; room temperature = 22 oC)
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Application of Quantum statistics

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-1.16

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In solid-state physics, the electronic
band structure (or simply band
structure) of a solid describes those
ranges of energy that an electron within
the solid may have (called energy
bands, allowed bands, or simply bands),
and ranges of energy that it may not
have (called band gaps or forbidden
bands).
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Band theory derives these bands and band gaps
by examining the allowed quantum
mechanical wave functions for an electron in a
large, periodic lattice of atoms or molecules.

Band theory has been successfully used to explain

many physical properties of solids, such as
electrical resistivity and optical absorption, and
forms the foundation of the understanding of
all solid-state devices (transistors, solar cells, etc.).

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- Normally a system can have many excited
states and many ground states.

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-how many particles can be in any quantum state? Total N is fixed

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https://www.youtube.com/watch?v=ZveSAb95iNo
Same goes to the y-portion and z-portion of KE and
x-portion and z-portion of PE.
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https://www.youtube.com/watch?v=B9ukqBYxIDs
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Average energy per
degree of freedom

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Energy and Quadratic Forms
A simple model of a crystal--masses m on springs with coefficients k.

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separation

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theoretically. 56
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Plot of molar heat capacity vs. temperature for a hypothetical non-
condensing diatomic gas in a typical room. The number of degrees of
freedom per molecule goes from 0 to 3 to 5 to 7, as the excitation
temperatures for translational, rotational, and vibrational motions are 60
passed.
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 THE END

A LITTLE CAPTION OF 63
TANGKUBAN PARAHU, INDONESIA (2009)