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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 ...
The equation predicts that for short range interactions, the equilibrium velocity distribution will follow a Maxwell–Boltzmann distribution. To the right is a molecular dynamics (MD) simulation in which 900 hard sphere particles are constrained to move in a rectangle.
The typical problem begins with a system for which the Hamiltonian is known, it is at a given temperature and it follows the Boltzmann statistics. To obtain the mean value of some macroscopic variable, say A, the general approach is to compute, over all the phase space, PS for simplicity, the mean value of A using the Boltzmann distribution:
Maxwell–Boltzmann statistics is used to derive the Maxwell–Boltzmann distribution of an ideal gas. However, it can also be used to extend that distribution to particles with a different energy–momentum relation, such as relativistic particles (resulting in Maxwell–Jüttner distribution), and to other than three-dimensional spaces.
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 general equation can then be written as [6] = + + (),. where the "force" term corresponds to the forces exerted on the particles by an external influence (not by the particles themselves), the "diff" term represents the diffusion of particles, and "coll" is the collision term – accounting for the forces acting between particles in collisions.
The Boltzmann distribution itself is one of the most important tools in applying statistical mechanics to real systems, as it massively simplifies the study of systems that can be separated into independent parts (e.g., particles in a gas, electromagnetic modes in a cavity, molecular bonds in a polymer).
This link is provided by Boltzmann's fundamental assumption written as S = k B ln Ω , {\displaystyle S=k_{\rm {B}}\ln \Omega ,} where k B is the Boltzmann constant , S is the classical thermodynamic entropy, and Ω is the number of microstates.