Nonequilibrium thermodynamics with binary quantum correlations

TL;DR

This paper develops a nonequilibrium thermodynamic framework incorporating quantum correlations and molecular contributions, extending classical kinetic theory to include two-particle effects and proving an extended H-theorem.

Contribution

It introduces a quantum kinetic approach that accounts for molecular correlations and derives explicit expressions for their thermodynamic contributions.

Findings

Molecular contributions to observables are expressed via scattering phase shifts.

The two-particle entropy form extends Landau's quasiparticle picture.

Boltzmann's H-theorem is proved with molecular entropy contributions.

Abstract

The balance equations for thermodynamic quantities are derived from the nonlocal quantum kinetic equation. The nonlocal collisions lead to molecular contributions to the observables and currents. The corresponding correlated part of the observables is found to be given by the rate to form a molecule multiplied with its lifetime which can be considered as collision duration. Explicit expressions of these molecular contributions are given in terms of the scattering phase shifts. The two-particle form of the entropy is derived. This extends the Landau quasiparticle picture by two-particle molecular contributions. There is a continuous exchange of correlations into kinetic parts condensing into the rate of correlated variables for energy and momentum. For the entropy, an explicit gain remains and Boltzmann's H-theorem is proved including the molecular parts of the entropy.