de Broglie Swapping Metadynamics for Quantum and Classical Sampling

J Chem Theory Comput. 2015 Nov 10;11(11):5114-9. doi: 10.1021/acs.jctc.5b00818. Epub 2015 Oct 23.

Abstract

This paper builds on our previous work on Path Integral Metadynamics [ Ruge et al. J. Chem. Theory Comput. 2015 , 11 , 1383 ] in which we have accelerated sampling in quantum systems described by Feynman's Path Integrals using Metadynamics. We extend the scope of Path Integral Metadynamics by combining it with a replica exchange scheme in which artificially enhanced quantum effects play the same role as temperature does in parallel tempering. Our scheme can be adapted so as to be used in an ancillary way to sample systems described by classical statistical mechanics. Contrary to Metadynamics and many other sampling methods no collective variables need to be defined. The method in its two variants, quantum and classical, is tested in a number of examples.