Dimension-Free Ergodicity of Path Integral Molecular Dynamics

Abstract

The quantum thermal average plays a central role in describing the thermodynamic properties of a quantum system. Path integral molecular dynamics (PIMD) is a prevailing approach for computing quantum thermal averages by approximating the quantum partition function as a classical isomorphism on an augmented space, enabling efficient classical sampling, but the theoretical knowledge of the ergodicity of the sampling is lacking. Parallel to the standard PIMD with $N$ ring polymer beads, we also study the Matsubara mode PIMD, where the ring polymer is replaced by a continuous loop composed of $N$ Matsubara modes. Utilizing the generalized $\Gamma$ calculus, we prove that both the Matsubara mode PIMD and the standard PIMD have uniform-in-$N$ ergodicity, i.e., the convergence rate towards the invariant distribution does not depend on the number of modes or beads $N$.