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Nonequilibrium Work Relation in Macroscopic System

We reconsider a well-known relationship between the fluctuation theorem and the second law of thermodynamics by evaluating a probability measure-valued process. In order to establish a bridge between microscopic and macroscopic behaviors, we consider the thermodynamic limit of a stochastic dynamical system following the fundamental procedure often used in statistical mechanics. The thermodynamic path characterizing a macroscopic dynamical behavior can be formulated as an infimum of the action functional for the probability measure-valued process. In our formulation, the second law of thermodynamics can be derived by symmetry of the action functional, which is generated from the fluctuation theorem. We find that our formulation not only confirms that the ordinary Jarzynski equality in the thermodynamic limit can be rederived, but also enables us to establish a nontrivial nonequilibrium work relation for metastable states.

preprint2013arXivOpen access
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