@article{ab6c2ce7b3154388b6deae7dbfcacf95,
title = "Solvent reaction coordinate for an SN2 reaction",
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.",
author = "Christian Leitold and Mundy, {Christopher J.} and Baer, {Marcel D.} and Schenter, {Gregory K.} and Baron Peters",
note = "Funding Information: This work was supported by the U.S. Department of Energy{\textquoteright}s (DOE) Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory (PNNL) is operated for the Department of Energy by Battelle. We acknowledge computer resources through PNNL{\textquoteright}s institutional computing (PIC), and all the simulations were run on PNNL{\textquoteright}s Constance cluster. B.P. and C.L. acknowledge financial support from the National Science Foundation Award No. 1465289 in the Division of Theoretical Chemistry. C.J.M. and G.K.S. were supported by the U.S. Department of Energy{\textquoteright}s (DOE) Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. M.D.B. was supported by the BES, Division of Materials Science and Engineering, Synthesis and Processing Sciences Program. Publisher Copyright: {\textcopyright} 2020 Author(s). Copyright: Copyright 2020 Elsevier B.V., All rights reserved.",
year = "2020",
month = jul,
day = "14",
doi = "10.1063/5.0002766",
language = "English (US)",
volume = "153",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "2",
}