On the flux-force partitioning and non-equilibrium thermodynamics near a steady state

摘要

The flux-force linear relationship is a basic building block in the development of irreversible thermodynamics near equilibrium. Here, we explore the fate of this relationship near a steady state in a finer detail by partitioning the fluxes and the forces into time-independent and time-dependent components. To this end, we use a master equation approach without assuming the condition of detailed balance. The connection of the flux-force components with various state functions and path functions provides a detailed picture of the variations of such quantities in terms of the deviation of probabilities from the steady state. Pilot calculations on an exactlysolvable case furnish insights into the energy-balance mechanism for non-equilibrium systems, revealing additionally how an out-of-equilibrium scenario can be favorable in realizing a minimized free energy state.