Coarse-graining involving virtual sites: Centers of symmetry coarse-graining

J Chem Phys. 2019 Apr 21;150(15):154103. doi: 10.1063/1.5067274.

Abstract

Coarse-grained (CG) models allow efficient molecular simulation by reducing the degrees of freedom in the system. To recapitulate important physical properties, including many-body correlations at the CG resolution, an appropriate mapping from the atomistic to CG level is needed. Symmetry exhibited by molecules, especially when aspherical, can be lost upon coarse-graining due to the use of spherically symmetric CG effective potentials. This mismatch can be efficiently amended by imposing symmetry using virtual CG sites. However, there has been no rigorous bottom-up approach for constructing a many-body potential of mean force that governs the distribution of virtual CG sites. Herein, we demonstrate a statistical mechanical framework that extends a mapping scheme of CG systems involving virtual sites to provide a thermodynamically consistent CG model in the spirit of the principle of maximum entropy. Utilizing the extended framework, this work defines a center of symmetry (COS) mapping and applies it to benzene and toluene systems such that the planar symmetry of the aromatic ring is preserved by constructing two virtual sites along a normal vector. Compared to typical center of mass (COM) CG models, COS CG models correctly recapitulate radial and higher order correlations, e.g., orientational and three-body correlations. Moreover, we find that COS CG interactions from bulk phases are transferable to mixture phases, whereas conventional COM models deviate between the two states. This result suggests a systematic approach to construct more transferable CG models by conserving molecular symmetry, and the new protocol is further expected to capture other many-body correlations by utilizing virtual sites.