Thermodynamics and stochastic thermodynamics of strongly coupled systems.

Abstract

We further develop the strong-coupling theory of thermodynamics and stochastic thermodynamics for continuous systems, constructed in the previous work [Phys. Rev. Res. 4, 013015 (2022)2643-156410.1103/PhysRevResearch.4.013015]. A small system strongly interacting with a its environment, the dynamics of the system is assumed to be much slower than that of the bath. The system Hamiltonian is defined to be the Hamiltonian of mean force, whereas the system entropy is defined as the Gibbs-Shannon entropy. Equilibrium ensemble theories and thermodynamic theories are established for the system. Variations of three types of parameters are considered: (i) the system parameter λ which couples to the system and to the interaction, (ii) the bath parameter λ^{'} which couples to the bath only, and (iii) the temperature T=1/β. The work done to the system consists of three parts, proportional to dλ,dλ^{'}, and dβ respectively. The part proportional to dβ can be understood as the work done by the bath. As long as λ^{'} and β are not fixed, the work is not the change of total energy of the joint system. The differences between our strong-coupling equilibrium thermodynamics and the classical thermodynamics are discussed. The thermodynamic theory is promoted to the nonequilibrium level. Both the first and second laws of thermodynamics, as well as fluctuation theorems, are established for nonequilibrium processes. For processes with varying temperatures, fluctuation theorems cannot be expressed in terms of integrated work alone. Regardless of various subtleties, however, the stochastic thermodynamic theory is formulated in terms of system variables only, and dS-βd[over ¯]Q is the change of total entropy. Thermodynamic quantities of the system are related to those of the joint system, and the equivalence of theories at two levels of coarse-graining is explicitly demonstrated. Finally we show that there are infinite numbers of equivalent strong-coupling theories, each determined by its definition of system Hamiltonian. Our theory is distinguished by its maximal similarity with the weak-coupling theory.