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As an example: the partition function for the isothermal-isobaric ensemble, the generalized Boltzmann distribution, divides up probabilities based on particle number, pressure, and temperature. The energy is replaced by the characteristic potential of that ensemble, the Gibbs Free Energy .
What has been presented above is essentially a derivation of the canonical partition function. As one can see by comparing the definitions, the Boltzmann sum over states is equal to the canonical partition function. Exactly the same approach can be used to derive Fermi–Dirac and Bose–Einstein statistics.
The partition function or configuration integral, as used in probability theory, information theory and dynamical systems, is a generalization of the definition of a partition function in statistical mechanics. It is a special case of a normalizing constant in probability theory, for the Boltzmann distribution.
The denominator in equation 1 is a normalizing factor so that the ratios : add up to unity — in other words it is a kind of partition function (for the single-particle system, not the usual partition function of the entire system).
Boltzmann's distribution is an exponential distribution. Boltzmann factor (vertical axis) as a function of temperature T for several energy differences ε i − ε j.. In statistical mechanics and mathematics, a Boltzmann distribution (also called Gibbs distribution [1]) is a probability distribution or probability measure that gives the probability that a system will be in a certain ...
rather than the free energy. The equations below (in terms of free energy) may be restated in terms of the canonical partition function by simple mathematical manipulations. Historically, the canonical ensemble was first described by Boltzmann (who called it a holode) in 1884 in a relatively unknown paper. [2]
The equation is a nonlinear integro-differential equation, and the unknown function in the equation is a probability density function in six-dimensional space of a particle position and momentum. The problem of existence and uniqueness of solutions is still not fully resolved, but some recent results are quite promising.
Boltzmann's entropy describes the system when all the accessible microstates are equally likely. ... is the microcanonical partition function is the canonical ...