Solvent reaction coordinate for an SN2 reaction

Christian Leitold, Christopher J. Mundy, Marcel D. Baer, Gregory K. Schenter, Baron Peters

Research output: Contribution to journalArticle

Abstract

We study the prototypical SN2 reaction Cl- + CH3Cl → CH3Cl + Cl- in water using quantum mechanics/molecular mechanics (QM/MM) computer simulations with transition path sampling and inertial likelihood maximization. We have identified a new solvent coordinate to complement the original atom-exchange coordinate used in the classic analysis by Chandrasekhar, Smith, and Jorgensen [J. Am. Chem. Soc. 107, 154 (1985)]. The new solvent coordinate quantifies instantaneous solvent-induced polarization relative to the equilibrium average charge density at each point along the reaction pathway. On the basis of likelihood scores and committor distributions, the new solvent coordinate improves upon the description of solvent dynamical effects relative to previously proposed solvent coordinates. However, it does not increase the transmission coefficient or the accuracy of a transition state theory rate calculation.

Original languageEnglish (US)
Article number024103
JournalJournal of Chemical Physics
Volume153
Issue number2
DOIs
StatePublished - Jul 14 2020

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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    Leitold, C., Mundy, C. J., Baer, M. D., Schenter, G. K., & Peters, B. (2020). Solvent reaction coordinate for an SN2 reaction. Journal of Chemical Physics, 153(2), [024103]. https://doi.org/10.1063/5.0002766