Quantum free-energy differences from nonequilibrium path integrals. II. Convergence properties for the harmonic oscillator.
Nonequilibrium path-integral methods for computing quantum free-energy differences are applied to a quantum particle trapped in a harmonic well of uniformly changing strength with the purpose of establishing the convergence properties of the work distribution and free energy as the number of degrees of freedom M in the regularized path integrals goes to infinity. The work distribution is found to converge when M tends to infinity regardless of the switching speed, leading to finite results for the free-energy difference when the Jarzynski nonequilibrium work relation or the Crooks fluctuation relation are used. The nature of the convergence depends on the regularization method. For the Fourier method, the convergence of the free-energy difference and work distribution go as 1/M , while both quantities converge as 1/M(2) when the bead regularization procedure is used. The implications of these results to more general systems are discussed.
van Zon
Ramses
R
Chemical Physics Theory Group, Department of Chemistry, University of Toronto, 80 Saint George Street, Toronto, Ontario, Canada.
Hernández de la Peña
Lisandro
L
Peslherbe
Gilles H
GH
Schofield
Jeremy
J