Real time quantum dynamics preaveraged over imaginary time path integral: A formal basis for both Centroid Molecular Dynamics and Ring Polymer Molecular Dynamics

Abstract

An exact real time quantum dynamics preaveraged over imaginary time path integral is formulated for general condensed phase equilibrium ensemble. This formulation results in the well-known centroid dynamics approach upon filtering of centroid constraint, and provides a rigorous framework to understand and analyze a related quantum dynamics approximation method called ring polymer molecular dynamics. The formulation also serves as the basis for developing new kinds of quantum dynamics that utilize the cyclic nature of the imaginary time path integral.