Macroscopic fluxes and local reciprocal relation in second-order stochastic processes far from equilibrium

TL;DR

This paper investigates second-order stochastic processes far from equilibrium, revealing a reciprocal relation between macroscopic fluxes and forces, and connecting thermal diffusion effects at the nanoscale.

Contribution

It establishes the reciprocal relation between fluxes and forces in second-order stochastic processes far from equilibrium, extending thermodynamic principles to nanoscale systems.

Findings

Macroscopic fluxes vanish at thermodynamic equilibrium, matching time-reversibility.

Entropy production rate aligns with classical expressions in the small noise limit.

Reciprocal relations hold for transient and steady states, proportional to local temperature squared over friction.

Abstract

Stochastic process is an essential tool for the investigation of the physical and life sciences at nanoscale. In the first-order stochastic processes widely used in chemistry and biology, only the flux of mass rather than that of heat can be well defined. Here we investigate the two macroscopic fluxes in second-order stochastic processes driven by position-dependent forces and temperature gradient. We prove that the thermodynamic equilibrium defined through the vanishing of macroscopic fluxes is equivalent to that defined via time reversibility at mesoscopic scale. In the small noise limit, we find that the entropy production rate, which has previously been defined by the mesoscopic irreversible fluxes on the phase space, matches the classic macroscopic expression as the sum of the products of macroscopic fluxes and their associated thermodynamic forces. Further we show that the two pairs of forces and fluxes in such a limit follow a linear phenomenonical relation and the associated scalar coefficients always satisfy the reciprocal relation for both transient and steady states. The scalar coefficient is proportional to the square of local temperature divided by the local frictional coefficient and originated from the second moment of velocity distribution along each dimension. This result suggests the very close connection between Soret effect (thermal diffusion) and Dufour effect at nano scale even far from equilibrium.