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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.
The Gibbs measure is also the unique measure that has the property of maximizing the entropy for a fixed expectation value of the energy; this underlies the appearance of the partition function in maximum entropy methods and the algorithms derived therefrom.
In thermodynamics, the Gibbs free energy (or Gibbs energy as the recommended name; symbol ) is a thermodynamic potential that can be used to calculate the maximum amount of work, other than pressure–volume work, that may be performed by a thermodynamically closed system at constant temperature and pressure.
In contrast, the Gibbs free energy or free enthalpy is most commonly used as a measure of thermodynamic potential (especially in chemistry) when it is convenient for applications that occur at constant pressure. For example, in explosives research Helmholtz free energy is often used, since explosive reactions by their nature induce pressure ...
The partition function for the ... From the preceding analysis it is clear that the characteristic state function of this ensemble is the Gibbs free energy, ...
Usually, the quantum states are discrete, even though there may be an infinite number of them. For a system with some specified energy E, one takes Ω to be the number of energy eigenstates within a macroscopically small energy range between E and E + δE. In the thermodynamical limit, the specific entropy becomes independent on the choice of δE.
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 ...
Several free energy functions may be formulated based on system criteria. Free energy functions are Legendre transforms of the internal energy. The Gibbs free energy is given by G = H − TS, where H is the enthalpy, T is the absolute temperature, and S is the entropy. H = U + pV, where U is the internal energy, p is the pressure, and V is the ...