TY - JOUR

T1 - Effect of configuration-dependent multi-body forces on interconversion kinetics of a chiral tetramer model

AU - Petsev, Nikolai D.

AU - Stillinger, Frank H.

AU - Debenedetti, Pablo G.

N1 - Funding Information:
The authors are grateful to Sergey Buldyrev for suggesting the presence of a configuration-dependent energy term as a possible source of non-conservative forces in the original model formulation and to Yiming Wang and Betul Uralcan for useful discussions regarding this work. The simulations presented in this article were performed on computational resources managed and supported by Princeton Research Computing, a consortium of groups including the Princeton Institute for Computational Science and Engineering (PICSciE) and the Office of Information Technology’s High Performance Computing Center and Visualization Laboratory at Princeton University. Molecular visualization was performed with the UCSF Chimera package. Chimera is developed by the Resource for Biocomputing, Visualization, and Informatics at the University of California, San Francisco (supported by NIGMS Grant No. P41-GM103311). P.G.D. gratefully acknowledges support from the National Science Foundation (Grant No. CHE-1856704).
Publisher Copyright:
© 2021 Author(s).

PY - 2021/8/28

Y1 - 2021/8/28

N2 - 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 λ, where λ < 0 favors local configurations involving tetramers of opposite chirality and λ > 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 λ ≠ 0 increases the effective barrier for enantiomer inversion. Our simulations reveal that for λ > 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.

AB - 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 λ, where λ < 0 favors local configurations involving tetramers of opposite chirality and λ > 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 λ ≠ 0 increases the effective barrier for enantiomer inversion. Our simulations reveal that for λ > 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.

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U2 - 10.1063/5.0060266

DO - 10.1063/5.0060266

M3 - Article

C2 - 34470355

AN - SCOPUS:85114107289

VL - 155

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 8

M1 - 084105

ER -