9 - Nonequilibrium fluctuations

Summary

Introduction

Nonequilibrium steady states are fascinating systems to study. Although there are many parallels between these states and equilibrium states, a convincing theoretical description of steady states, particularly far from equilibrium, has yet to be found. Close to equilibrium, linear response theory and linear irreversible thermodynamics provide a relatively complete treatment, (Sections 2.1 to 2.3). However, in systems where local thermodynamic equilibrium has broken down, and thermodynamic properties are not the same local functions of thermodynamic state variables that they are at equilibrium, our understanding is very primitive indeed.

In Section 7.3 we gave a statistical-mechanical description of thermostatted, nonequilibrium steady states far from equilibrium — the transient time-correlation function (TTCF) and Kawasaki formalisms. The transient time-correlation function is the nonlinear analog of the Green—Kubo correlation functions. For linear transport processes the Green—Kubo relations play a role which is analogous to that of the partition function at equilibrium. Like the partition function, Green—Kubo relations are highly nontrivial to evaluate. They do, however, provide an exact starting point from which one can derive exact interrelations between thermodynamic quantities. The Green—Kubo relations also provide a basis for approximate theoretical treatments as well as being used directly in equilibrium molecular-dynamics simulations.

The TTCF and Kawasaki expressions may be used as nonlinear, nonequilibrium partition functions.