Effect of configuration-dependent multi-body forces on interconversion kinetics of a chiral tetramer model

ND Petsev and FH Stillinger and PG Debenedetti, JOURNAL OF CHEMICAL PHYSICS, 155, 084105 (2021).

DOI: 10.1063/5.0060266

We describe a reformulation of the four-site molecular model for chiral phenomena introduced by Latinwo et al. "Molecular model for chirality phenomena," J. Chem. Phys. 145, 154503 (2016). The reformulation includes an additional eight-body force that arises from an explicit configuration-dependent term in the potential energy function, resulting in a coarse-grained energy-conserving force field for molecular dynamics simulations of chirality phenomena. In this model, the coarse-grained interaction energy between two tetramers depends on their respective chiralities and is controlled by a parameter lambda, where lambda < 0 favors local configurations involving tetramers of opposite chirality and lambda > 0 gives energetic preference to configurations involving tetramers of the same chirality. We compute the autocorrelation function for a quantitative chirality metric and demonstrate that the multi-body force modifies the interconversion kinetics such that lambda not equal 0 increases the effective barrier for enantiomer inversion. Our simulations reveal that for lambda > 0 and temperatures below a sharply defined threshold value, this effect is dramatic, giving rise to spontaneous chiral symmetry breaking and locking molecules into their chiral identity. Published under an exclusive license by AIP Publishing.

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