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From the statistical mechanical viewpoint, relaxation of macroscopic systems and response theory rest on a notion of typicality, according towhich the behavior of singlemacroscopic objects is given by appropriate ensembles: ensemble averages of observable quantities represent the measurements performed on single objects, because “almost all” objects share the same fate. In the case of non-dissipative dynamics and relaxation toward equilibrium states, “almost all” is referred to invariant probability distributions that are absolutely continuous with respect to the Lebesgue measure. In otherwords, the collection of initialmicro-states (single systems) that do not follow the ensemble is supposed to constitute a set of vanishing, phase space volume. This approach is problematic in the case of dissipative dynamics and relaxation to nonequilibrium steady states, because the relevant invariant distributions attribute probability 1 to sets of zero volume, while evolution commonly begins in equilibrium states, i.e., in sets of full phase space volume. We consider the relaxation of classical, thermostatted particle systems to nonequilibrium steady states. We show that the dynamical condition known as T-mixing is necessary and sufficient for relaxation of ensemble averages to steady state values. Moreover, we find that the condition known as weak T-mixing applied to smooth observables is sufficient for ensemble relaxation to be independent of the initial ensemble. Lastly, we show that weak T-mixing provides a notion of typicality for dissipative dynamics that is based on the (non-invariant) Lebesgue measure, and that we call physical ergodicity.

Using the Fluctuation Theorem (FT), we give a first-principles derivation of Boltzmann’s postulate of equal a priori probability in phase space for the microcanonical ensemble. Using a corollary of the Fluctuation Theorem, namely the Second Law Inequality, we show that if the initial distribution differs from the uniform distribution over the energy hypersurface, then under very wide and commonly satisfied conditions, the initial distribution will relax to that uniform distribution. This result is somewhat analogous to the Boltzmann H-theorem but unlike that theorem, applies to dense fluids as well as dilute gases and also permits a nonmonotonic relaxation to equilibrium. We also prove that in ergodic systems the uniform (microcanonical) distribution is the only stationary, dissipationless distribution for the constant energy ensemble.