Unified theory of thermodynamics and stochastic thermodynamics for nonlinear Langevin systems driven by non-conservative forces

Abstract

We construct a unified theory of thermodynamics and stochastic thermodynamics for classical nonequilibrium systems driven by non-conservative forces, using the recently developed covariant Ito-Langevin theory. The thermodynamic forces are split into a conservative part and a non-conservative part. Thermodynamic functions are defined using the reference conservative system. Work and heat are partitioned into excess parts and house-keeping parts, which are due to, respectively, conservative forces and non-conservative forces. Excess entropy production (EP) and house-keeping EP are analogously defined. The splitting of thermodynamic forces is subjected to an arbitrariness resembling a gauge symmetry, with each gauge defining a reference conservative Langevin system. In the special Gibbs gauge, the nonequilibrium steady state (NESS) is characterized by Gibbs canonical distribution, the excess heat agrees with that defined by Hatano and Sasa, and the excess EP agrees with that of Glansdorff and Prigogine, i.e., it is the time rate of the second-order variation of system entropy near the NESS. Adopting the Gibbs gauge, and focusing on the excess parts of thermodynamic quantities, a complete analogy between thermodynamics of non-conservative systems and that of conservative systems is established. One important consequence of this analogy is that both the free energy and excess EP are minimized at NESS. Our theory therefore constitutes a statistical foundation both for the steady-state thermodynamics theory due to Sasa and Tasaki and for the stability theory of NESS due to Glansdorff and Prigogine. These results are valid even if the system is far from equilibrium. By studying detailed fluctuation theorem, we find striking differences between systems with symmetric kinetic matrices and those with asymmetric kinetic matrices. For systems with asymmetric kinetic matrices, the total EP is the sum of house-keeping EP, excess EP, and pumped entropy. Entropy pumping is an exchange of entropy between the system and environment without necessarily involving dissipation. In the presence of entropy pumping, the system may behave as either a demon or an antidemon. Fluctuation theorems and work relations are derived both for total work and for excess work. For systems with symmetric kinetic matrices, there is no entropy pumping, yet in the Gibbs gauge, the excess work and house-keeping work each satisfies a separate fluctuation theorem. We illustrate our theory using many concrete examples.