Free energy differences from nonequilibrium work distributions: ⟨e−W/kT⟩ = e−ΔF/kT
Jarzynski (1997) proved that for ANY nonequilibrium protocol connecting two states, an exponential average of the work W done on the system equals the equilibrium free energy difference ΔF:
This holds regardless of how fast the protocol is. Slow protocols cluster near ΔF; fast ones spread widely. Crucially, rare trajectories with W < ΔF (entropy-consuming) dominate the average and pull it down to the correct equilibrium value.