Relative Resolution: An Analysis with the Kullback-Leibler Entropy.

Abstract

A novel type of a multiscale approach, called Relative Resolution (RelRes), can correctly retrieve the behavior of various nonpolar liquids while speeding up molecular simulations by almost an order of magnitude. In this approach in a single system, molecules switch their resolution in terms of their relative separation, with near neighbors interacting via fine-grained potentials, yet far neighbors interacting via coarse-grained potentials; notably, these two potentials are analytically parametrized by a multipole approximation. Our current work focuses on analyzing RelRes by relating it with the Kullback-Leibler (KL) entropy, which is a useful metric for multiscale errors. In particular, we thoroughly examine the exact and approximate versions of this informatic measure for several alkane systems. By analyzing its dependency on the system size, we devise a formula for predicting the exact KL entropy of an "infinite" system via the computation of the approximate KL entropy of an "infinitesimal" system. Demonstrating that the KL entropy can holistically capture many multiscale errors, we settle bounds for the KL entropy that ensure a sufficient representation of the structural and thermal behavior by the RelRes algorithm. This, in turn, allows the scientific community to readily determine the ideal switching distance for an arbitrary RelRes system.