Stochastic and macroscopic thermodynamics of strongly coupled systems

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We develop a thermodynamic framework that describes a classical system of interest S that is strongly coupled to its thermal environment E. Within this framework, seven key thermodynamic quantities— internal energy, entropy, volume, enthalpy, Gibbs free energy, heat, and work—are defined microscopi- cally. These quantities obey thermodynamic relations including both the first and second law, and they satisfy nonequilibrium fluctuation theorems.We additionally impose a macroscopic consistency condition: When S is large, the quantities defined within our framework scale up to their macroscopic counterparts. By satisfying this condition, we demonstrate that a unifying framework can be developed, which encompasses both stochastic thermodynamics at one end, and macroscopic thermodynamics at the other. A central element in our approach is a thermodynamic definition of the volume of the system of interest, which converges to the usual geometric definition when S is large.We also sketch an alternative framework that satisfies the same consistency conditions. The dynamics of the system and environment are modeled using Hamilton’s equations in the full phase space. DOI:

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Jarzynski, C. (2017). Stochastic and macroscopic thermodynamics of strongly coupled systems. Physical Review X, 7(1).

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