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Thermal Contact I : Symmetries ruled by Exchange Entropy Variations

Thermal contact is the archetype of non-equilibrium processes driven by constant non-equilibrium constraints enforced by reservoirs exchanging conserved microscopic quantities. In models with a finite number of possible configurations, if the microscopic dynamics is assumed to be deterministic and ergodic and to conserve energy according to some specific pattern, and if the mesoscopic evolution of the global system is approximated by a Markov process as closely as possible, then the mesoscopic transition rates obey three constraints. In the limit where macroscopic bodies can be considered as reservoirs at thermodynamic equilibrium (but with different intensive parameters) the third constraint becomes modified detailed balance (MDB) ; the latter is generically expressed in terms of the microscopic exchange entropy variation. We investigate the generic statistical properties for measurable quantities that arise from the MDB constraint. For a finite-time evolution after the system prepared in an equilibrium state has been set in contact with thermostats at different temperatures, we derive a detailed fluctuation relation for the excess exchange entropy variation. In the non-equilibrium stationary state (long-time limit), the proper mathematical definition of a large deviation function is introduced together with alternative definitions, and fluctuation relations are rederived. The generalization to systems exchanging energy, volume and matter with several reservoirs, with a possible conservative external force acting on the contact system, is given explicitly. The infinite time limit of any odd cumulant per unit time of exchanged quantities is expressed in terms of a series involving higher even cumulants and powers of the thermodynamic forces associated to independent mean currents.