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Effect of configuration-dependent multi-body forces on interconversion kinetics of a chiral tetramer model.
Petsev, Nikolai D; Stillinger, Frank H; Debenedetti, Pablo G.
Afiliación
  • Petsev ND; Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544, USA.
  • Stillinger FH; Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
  • Debenedetti PG; Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544, USA.
J Chem Phys ; 155(8): 084105, 2021 Aug 28.
Article en En | MEDLINE | ID: mdl-34470355
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.

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Chem Phys Año: 2021 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Chem Phys Año: 2021 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos