The intrinsic non-equilibrium nature of thermophoresis

TL;DR

This paper demonstrates that thermophoresis is a fundamental non-equilibrium phenomenon arising from temperature-dependent internal state transitions with different transport properties, providing a thermodynamic framework and a new expression for the Soret coefficient.

Contribution

It introduces a thermodynamically consistent model showing thermophoresis as a non-equilibrium effect driven by internal state transitions modulated by temperature.

Findings

Thermophoresis occurs in systems with temperature-dependent internal states.

The Soret coefficient relates to energy-transport correlations of internal states.

The approach generalizes previous close-to-equilibrium theories.

Abstract

Exposing a solution to a temperature gradient can lead to the accumulation of particles on either the cold or warm side. This phenomenon, known as thermophoresis, has been discovered more than a century ago, and yet its microscopic origin is still debated. Here, we show that thermophoresis can be observed in any system such that the transitions between different internal states are modulated by temperature and such that different internal states have different transport properties. We establish thermophoresis as a genuine non-equilibrium effect, whereby a system of currents in real and internal space that is consistent with the thermodynamic necessity of transporting heat from warm to cold regions. Our approach also provides an expression for the Soret coefficient, which decides whether particles accumulate on the cold or on the warm side, that is associated with the correlation between the energies of the internal states and their transport properties, that instead remain system-specific quantities. Finally, we connect our results to previous approaches based on close-to-equilibrium energetics. Our thermodynamically consistent approach thus encompasses and generalizes previous findings.