Understanding three-body contributions to coarse-grained force fields

C Scherer and D Andrienko, PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 20, 22387-22394 (2018).

DOI: 10.1039/c8cp00746b

D Coarse-graining is a systematic reduction of the number of degrees of freedom used to describe a system of interest. Coarse-graining can be thought of as a projection on the coarse-grained degrees of freedom and is therefore dependent on the number and type of basis functions used to represent the coarse-grained force field. We show that many-body extensions of the coarse-grained force field can result in substantial changes of the two-body interactions, making them much more attractive at short distances. This interplay can be alleviated by first parametrizing the two-body potential and then fitting the additional three-body contribution to the residual forces. The approach is illustrated on liquid water where three-body interactions are essential to reproduce the structural properties, and liquid methanol where two- body interactions are sufficient to reproduce the main structural features of the atomistic system. Furthermore, we demonstrate that the structural and thermodynamic accuracy of the coarse-grained models can be controlled by varying the magnitude of the three-body interactions. Our findings motivate basis set extensions which separate the many-body contributions of different order.

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