A microcanonical approach to temperature-transferable coarse-grained models using the relative entropy

E Pretti and MS Shell, JOURNAL OF CHEMICAL PHYSICS, 155, 094102 (2021).

DOI: 10.1063/5.0057104

Bottom-up coarse-graining methods provide systematic tools for creating simplified models of molecular systems. However, coarse-grained (CG) models produced with such methods frequently fail to accurately reproduce all thermodynamic properties of the reference atomistic systems they seek to model and, moreover, can fail in even more significant ways when used at thermodynamic state points different from the reference conditions. These related problems of representability and transferability limit the usefulness of CG models, especially those of strongly state-dependent systems. In this work, we present a new strategy for creating temperature-transferable CG models using a single reference system and temperature. The approach is based on two complementary concepts. First, we switch to a microcanonical basis for formulating CG models, focusing on effective entropy functions rather than energy functions. This allows CG models to naturally represent information about underlying atomistic energy fluctuations, which would otherwise be lost. Such information not only reproduces energy distributions of the reference model but also successfully predicts the correct temperature dependence of the CG interactions, enabling temperature transferability. Second, we show that relative entropy minimization provides a direct and systematic approach to parameterize such classes of temperature-transferable CG models. We calibrate the approach initially using idealized model systems and then demonstrate its ability to create temperature-transferable CG models for several complex molecular liquids.& nbsp;Published under an exclusive license by AIP Publishing.

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