Investigation of Coarse-Grained Mappings via an Iterative Generalized Yvon–Born–Green Method

Low resolution coarse-grained (CG) models enable highly efficient simulations of complex systems. The interactions in CG models are often iteratively refined over multiple simulations until they reproduce the one-dimensional (1-D) distribution functions, e.g., radial distribution functions (rdfs), of an all-atom (AA) model. In contrast, the multiscale coarse-graining (MS-CG) method employs a generalized Yvon–Born–Green (g-YBG) relation to determine CG potentials directly (i.e., without iteration) from the correlations observed for the AA model. However, MS-CG models do not necessarily reproduce the 1-D distribution functions of the AA model. Consequently, recent studies have incorporated the g-YBG equation into iterative methods for more accurately reproducing AA rdfs. In this work, we consider a theoretical framework for an iterative g-YBG method. We numerically demonstrate that the method robustly determines accurate models for both hexane and also a more complex molecule, 3-hexylthiophene. By examining the MS-CG and iterative g-YBG models for several distinct CG representations of both molecules, we investigate the approximations of the MS-CG method and their sensitivity to the CG mapping. More generally, we explicitly demonstrate that CG models often reproduce 1-D distribution functions of AA models at the expense of distorting the cross-correlations between the corresponding degrees of freedom. In particular, CG models that accurately reproduce intramolecular 1-D distribution functions may still provide a poor description of the molecular conformations sampled by the AA model. We demonstrate a simple and predictive analysis for determining CG mappings that promote an accurate description of these molecular conformations.