Equations of motion for position-dependent coarse-grain mappings obtained with Mori-Zwanzig theory.

Abstract

A position-dependent transformation is introduced for mapping a system of atomistic particles to a system of coarse-grained (CG) variables, which under some circumstances might be considered particles. This CG mapping allows atomistic particles to simultaneously contribute to more than a single CG particle and to change in time the CG particle they are associated with. That is, the CG mapping is dynamic. Mori-Zwanzig theory is then used to obtain the equations of motion for this CG mapping, resulting in conservative, dissipative, and random force terms in generalized, non-Markovian Langevin equations. In addition to the usual forces arising from the effective CG potential derived from atomistic interactions, new forces arise from the dynamic changes in the CG mapping itself. These new forces effectively account for changes arising from fluxes of atomistic particles into and out of CG ones as time progresses. Several examples are given showing the range of problems that can be addressed with this new CG mapping. These range from the usual case where atomistic particles are grouped into large molecular-like chunks, with mappings that remain fixed in time and for which an atomistic particle is part of only a single CG one, to the case where CG particles resemble fluid elements, containing many hundreds of independent atomistic particles. The new CG mapping also allows for hybrid descriptions, in which a part of the system remains atomistic or molecular-like and a part is highly coarse-grained to mesoscopic fluid element-like particles, for example. In the latter case, the equations of motion then provide the correct formalism for determining the forces, beyond the usual conservative ones. This provides a theoretical foundation upon which approximate equations of motion can be formulated to thus build numerical algorithms for expanded applications of accurate CG molecular dynamics.