Path Integral Coarse-Graining Replica Exchange Method for Enhanced Sampling.

An enhanced conformational space sampling method is developed that utilizes replica exchange molecular dynamics between a set of imaginary time Feynman path integral replicas, each having an increasing degree of contraction (or coarse-graining) of the quasi-particle or “polymer beads” in the evaluation of the isomorphic ring-polymer potential energy terms. However, there is no contraction of beads in the effectively harmonic kinetic energy terms. The final replica in this procedure is the fully contracted one in which the potential energy is evaluated only at the centroid of the beads—and hence it is the classical distribution in the centroid variable—while the initial replica has the full degree (or even a heightened degree, if desired) of quantum delocalization and tunneling in the physical potential by the polymer necklace beads. The exchange between the different ring-polymer ensembles is governed by the Metropolis criteria to guarantee detailed balance. The method is applied successfully to several m...