Nonperturbative computation of thermal conductivity based on Path Integral Monte Carlo methods

Abstract

The calculation of thermal conductivity in insulating solids at temperatures below the Debye temperature is problematic, due to the breakdown of classical and semi-classical approaches. In this work, we present a fully non-perturbative quantum methodology to compute thermal conductivity based on Path Integral Monte Carlo (PIMC) simulations combined with the Green-Kubo linear response theory. The method is applied to rare gas solids modeled by a Lennard-Jones potential, paradigmatic systems where quantum effects strongly affect both thermodynamic and transport properties. From PIMC simulations, we obtain the temperature-dependent phonon frequencies, lifetimes, and specific heat. From the imaginary time correlations of the energy current, we extract the thermal transport coefficients based on a physically motivated prior. We show that the experimentally observed increase of the thermal conductivity of argon and neon at low temperatures cannot be explained within a Peierls-Boltzmann framework using phonon line-widths at equilibrium. In contrast, a distinct transport lifetime emerges from the analysis of heat-current correlations. Our results demonstrate that quantum Monte Carlo methods provide a robust, nonperturbative framework to investigate heat transport in insulating solids, beyond the limits of classical molecular dynamics without relying on perturbative or semi-classical approximations.