Quantum free-energy differences from nonequilibrium path integrals. I. Methods and numerical application.

In this paper, the imaginary-time path-integral representation of the canonical partition function of a quantum system and nonequilibrium work fluctuation relations are combined to yield methods for computing free-energy differences in quantum systems using nonequilibrium processes. The path-integral representation is isomorphic to the configurational partition function of a classical field theory, to which a natural but fictitious Hamiltonian dynamics is associated. It is shown that if this system is prepared in an equilibrium state, after which a control parameter in the fictitious Hamiltonian is changed in a finite time, then formally the Jarzynski nonequilibrium work relation and the Crooks fluctuation relation hold, where work is defined as the change in the energy as given by the fictitious Hamiltonian. Since the energy diverges for the classical field theory in canonical equilibrium, two regularization methods are introduced which limit the number of degrees of freedom to be finite. The numerical applicability of the methods is demonstrated for a quartic double-well potential with varying asymmetry. A general parameter-free smoothing procedure for the work distribution functions is useful in this context.