Abstract

We present a generalization of Jarzynski's equality, applicable to quantum systems, that is related to discretized mechanical work and free-energy changes. The theory is based on a stepwise pulling protocol. We find that work distribution functions can be constructed from fluctuations of a reaction coordinate along a reaction pathway in the stepwise pulling protocol. We also propose two sets of equations to determine the two possible optimal pathways that provide the most significant contributions to free-energy changes. We find that the transitions along these most optimal pathways, satisfying both sets of equations, follow the principle of detailed balance. We then test the theory by explicitly computing the free-energy changes for a one-dimensional quantum harmonic oscillator. This approach suggests a feasible way of measuring the fluctuations to experimentally test Jarzynski's equality in many-body systems, such as Bose-Einstein condensates.

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