Boltzmann distribution
In statistical mechanics and mathematics, a Boltzmann distribution (also called Gibbs
distribution”) is a probability di ion, probability measure, or frequency distribution of particles
in a system over various possible states. The distribution is expressed in the form
x
F(state} xe FF
where £ is state energy (which varies from state to state), and A’ (a constant of the
distribution) is the product ofBaltzmann’s constant and thermodynamic temperature,
The ratio of a Boltzmann distribution computed for two states is known as the Boltzmann
factor and characteristically only depends on the states' energy difference.
F(state2) Ey Eo
ae ¥F
F(statel)
‘The Boltzmann distribution is named after Ludwig Boltzmann who first formulated it in 1868
during his studies of thestatistical mechanics of gases in thermal equiliorium "2 The
distribution was later investigated extensively, in its modern generic form, by Josiah Willard
Gibbs in 1902.22"
1 In statistical mechanics
2In mathematics
3 See also
4 References
In statistical mechanicsjedit
Main articles: Canonical ensemble end Maxweli—Boltzmann statistics
‘The Boltzmann distribution appears in statistical mechanics when considering isolated (or
neariy-isolated) systems of fixed composition that are in thermal equilibrium (equilibrium with
respect to energy exchange). The most general case is the probability distribution for the
‘canonical ensemble, but also some special cases (derivable from the canonical ensemble)
also show the Boltzmann distribution in different aspects:
Canonical ensemble (general case)
The canonical ensemble gives the probabilities of the various possible states of an isolated
system of fixed composition, in thermal equiliorium with a heat bath, The canonical ensemble
isa probability distribution with the Boltzmann form.
Statistical frequencies of subsystems' states (in a non-interacting collection)
When the system of interest is a collection of many non-interacting copies of a smaller
subsystem, it is sometimes useful to find the statistical frequency of a given subsystem stato,
among the collection. The canonical ensemble has the property of separability when applied
to such a collection: as long as the non-interacting subsystems have fixed composition, then
each subsystem's state is independent of the others and is also characterized by a canonical
ensemble. As @ result, the expected statistical frequency distribution of subsystem states has
the Boltzmann form.
Maxwoll-Boltzmann statistics of classical gases (systems of non-interacting
particles)
In particle systems, many particles share the same space and regularly change places with
each other, the single-particle state space they occupy is a shared space. Maxwel
Boltzmann statistics give the expected number of particles found in a given single-particlestate, in a classical gas of non-interacting particles at equilibrium. This expected number
distribution has the Boltzmann form.
Although these cases have strong similarities, itis helpful to distinguish them as
they generalize in different ways when the crucial assumptions are changed:
+ When a system is in thermodynamic equilibrium with respect to both energy
exchange and particle exchange, the requirement of fixed composition is
relaxed and a grand canonical ensemble is obtained rather than canonical
ensemble. On the other hand if both composition and energy are fixed, then
a microcanonical ensemble applies instead.
+ Ifthe subsystems within a collection do interact with each other, then the
expected frequencies of subsystem states no longer follow a Boltzmann
distribution, and even may not have an analytical solution.” The canonical
ensemble can however stil be applied to the collective states of the entire
system considered as a whole, provided the entire system is isolated and in
thermal equilibrium,
+ With quantum gases of non-interacting particles in equilibrium, the number
of particles found in a given single-particle state does not follow Maxwell
Boltzmann statistics, and there is no simple closed form expression for
quantum gases in the canonical ensemble. in the grand canonical
ensemble the state-filing statistics of quantum gases are described
byFermi—Dirac statistics or Bose-Einstein statistics, depending on whether
the particles are fermions or bosonsrespectively.
In mathematics
Main articles: Gibbs measure and Log-linear model
In more general mathematical settings, the Boltzmann distribution is also known
as the Gibbs measure. In statistics andmachine teaming it is called a log-linear
model