Non-Equilibrium Liouville and Wigner Equations: Classical Statistical Mechanics and Chemical Reactions for Long Times

Abstract

We review and improve previous work on non-equilibrium classical and quantum statistical systems, subject to potentials, without ab initio dissipation. We treat classical closed three-dimensional many-particle interacting systems without any “heat bath” ( h b ), evolving through the Liouville equation for the non-equilibrium classical distribution W c , with initial states describing thermal equilibrium at large distances but non-equilibrium at finite distances. We use Boltzmann’s Gaussian classical equilibrium distribution W c , e q , as weight function to generate orthogonal polynomials ( H n ’s) in momenta. The moments of W c , implied by the H n ’s, fulfill a non-equilibrium hierarchy. Under long-term approximations, the lowest moment dominates the evolution towards thermal equilibrium. A non-increasing Liapunov function characterizes the long-term evolution towards equilibrium. Non-equilibrium chemical reactions involving two and three particles in a h b are studied classically and quantum-mechanically (by using Wigner functions W). Difficulties related to the non-positivity of W are bypassed. Equilibrium Wigner functions W e q generate orthogonal polynomials, which yield non-equilibrium moments of W and hierarchies. In regimes typical of chemical reactions (short thermal wavelength and long times), non-equilibrium hierarchies yield approximate Smoluchowski-like equations displaying dissipation and quantum effects. The study of three-particle chemical reactions is new.