The often used analytical representation of the Maxwell–Boltzmann classical speed distribution function (
F) for elastic, indivisible particles assumes an infinite limit for the speed. Consequently, volume and the number of particles (
n) extend to infinity: Both infinities contradict assumptions
[...] Read more.
The often used analytical representation of the Maxwell–Boltzmann classical speed distribution function (
F) for elastic, indivisible particles assumes an infinite limit for the speed. Consequently, volume and the number of particles (
n) extend to infinity: Both infinities contradict assumptions underlying this non-relativistic formulation. Finite average kinetic energy and temperature (
T) result from normalization of
F removing
n: However, total energy (i.e., heat of the collection) remains infinite because
n is infinite. This problem persists in recent adaptations. To better address real (finite) systems, wherein
T depends on heat, we generalize this one-parameter distribution (
F, cast in energy) by proposing a two-parameter gamma distribution function (
F*) in energy which reduces to
F at large
n. Its expectation value of
kT (
k = Boltzmann’s constant) replicates
F, whereas the shape factor depends on
n and affects the averages, as expected for finite systems. We validate
F* via a first-principle, molecular dynamics numerical model of energy and momentum conserving collisions for 26, 182, and 728 particles in three-dimensional physical space. Dimensionless calculations provide generally applicable results; a total of 10
7 collisions suffice to represent an equilibrated collection. Our numerical results show that individual momentum conserving collisions in three-dimensions provide symmetrical speed distributions in all Cartesian directions. Thus, momentum and energy conserving collisions are the physical cause for equipartitioning of energy: Validity of this theorem for other systems depends on their specific motions. Our numerical results set upper limits on kinetic energy of individual particles; restrict the
n particles to some finite volume; and lead to a formula in terms of
n for conserving total energy when utilizing
F* for convenience. Implications of our findings on matter under extreme conditions are briefly discussed.
Full article