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Transcript
Defintion
The partition function Z is an important quantity that
encodes the statistical properties of a system in
thermodynamic equilibrium.
It is a function of temperature and other parameters,
such as the volume enclosing a gas.
Types of partition function
1.Canonical partition function
2. Grand canonical partition function
1. Canonical partition function
o1.1 Definition
o1.2 Meaning and significance
o1.3 Relation to thermodynamic variables
Definition
Suppose we have a thermodynamically large system that
is in constant thermal contact with the environment,
which has temperature T, with both the volume of the
system and the number of constituent particles fixed. This
kind of system is called a canonical ensemble.
The canonical partition function is
where the "inverse temperature" β is conventionally defined as
with kB denoting Boltzmann's constant .
In classical statistical mechanics :
where h is some infinitesimal quantity with units of action (usually
taken to be Planck's constant
H is the classical Hamiltonian
In quantum mechanics, the partition function is
where H is the quantum Hamiltonian operator
Meaning and significance
The partition function can be related to thermodynamic properties because
it has a very important statistical meaning. The probability Pj that the
system occupies microstate j is
This is the well-known Boltzmann factor
.) The partition function thus plays the role of a normalizing constant (note
that it does not depend on j),
Relation to thermodynamic
variables
The relationships between the partition function and the various
thermodynamic parameters of the system. These results can be derived
using the method of the previous section and the various thermodynamic
relations.
the thermodynamic energy is
The variance in the energy (or "energy fluctuation") is
The heat capacity is
The entropy is
Where F is the Helmholtz free energy defined as F = E - TS, where
E is the total energy and S is the entropy, so that
2 Grand canonical partition function
o
o2.1 Definition
2.2 Relation to thermoynamic
variables
o2.3 Discussion
Definition
can define a grand canonical partition function for a
grand canonical ensemble, a system that can exchange
both heat and particles with the environment, which has a
constant temperature T, volume V, and chemical potential
μ.
The grand canonical partition function for an ideal quantum gas is
written:
Relation to thermodynamic
variables
the canonical partition function, the grand canonical partition function can
be used to calculate thermodynamic and statistical variables of the system.
Defining α=-βμ, the most probable occupation numbers are:
Total number of particles
Variance in total number of particles
Internal energy
Variance in internal energy
Pressure
Mechanical equation of state
Discussion
Before specific results can be obtained from the grand canonical partition
function, the energy levels of the system under consideration need to
be specified. For example, the particle in a box model or particle in a
harmonic oscillator well provide a particular set of energy levels and
are a convenient way to discuss the properties of a quantum fluid.
(See the gas in a box and gas in a harmonic trap articles for a
description of quantum fluids.) These results may be used to
construct the grand partition function to describe an ideal Bose gas or
Fermi gas, and can be used as well to describe a classical ideal gas.