Statistical Mechanics of Thermal Diffusion in Rough Energy Landscapes

Abstract

Starting from a variational principle for mass transport, we present a broadly applicable statistical framework describing thermal diffusion in complex solids. We show that microscopic thermodynamic and kinetic fluctuations govern non-Arrhenius diffusion, with kinetic terms described by machine-learnable relative diffusion contributions. For vacancy diffusion in solid solutions, deviation from Arrheniusness may occur when ordering effects start to become important but at higher temperatures, approximately Arrhenius behavior can occur, aided by configurational entropy and competing energy fluctuations.