Jarzynski on work and free energy relations: The case of variable volume

Derivations of the Jarzynski equality (JE) appear to be quite general, and applicable to any particle system, whether deterministic or stochastic, under equally general perturbations of an initial equilibrium state at given temperatureT. At the same time, the definitions of the quantities appearing in the JE, in particular the work, have been questioned. Answers have been given, but a deeper understanding of the range of phenomena to which the JE applies is necessary, both conceptually and in order to interpret the experiments in which it is used. In fact, domains in which the JE is not applicable have been identified. To clarify the issue, we scrutinize the applicability of the JE to a Hamiltonian particle system in a variable volume. We find that, in this case, the standard interpretation of the terms appearing in the JE is not adequate.