Application range of Jarzynski’s equation for boundary-switching processes
Jarzynski’s equation(JE) has been known to relate free energy change of a system to statistical distribution of work done on the system for an arbitrary process. In the present work, we first establish the validity condition of JE for boundary switching processes. The validity condition of JE is examined for an example of spontaneous irreversible processes, for which, obviously, JE does not hold. We find that the free energy difference between two configurational states with different phase-space volume cannot be correctly estimated by JE for any adiabatic boundary switching process.