Polymeric Structural Symmetry Breaking and Conformational Search Driven by Anisotropic Dispersion Interactions

The modeling of conformations and dynamics of (bio)polymers is of primary importance for understanding physicochemical properties of soft matter. Although short-range interactions such as covalent and hydrogen bonding control the local arrangement of polymers, non-covalent interactions play a dominant role in determining the global conformations. Here we focus on how the inclusion of many-body effects [1] in van der Waals dispersion affects the outcome of the geometry optimization and molecular dynamics simulations of model polymers. We find that delocalized force contributions are key to explore the conformational landscape, as they induce an anisotropic polarization response which efficiently guides the conformation towards globally optimized structures. This is in contrast with the commonly used pair-wise approach, where the structure-independent atomic polarizabilities lack information on the global geometry. We show that such local approximation causes the conformational search to be obstructed by conformations with unphysically limited spatial symmetry, while the many-body formalism strongly reduces the roughness of the potential energy landscape.

[1] A. Tkatchenko et al, PRL 108, 236492 (2012).

[2] M. Galante and A. Tkatchenko, (2021) http://arxiv.org/abs/2110.06646 .