Solvent reaction coordinate for an SN2 reaction.
J Chem Phys
; 153(2): 024103, 2020 Jul 14.
Article
en En
| MEDLINE
| ID: mdl-32668925
ABSTRACT
We study the prototypical SN2 reaction Cl- + CH3Cl â 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.
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1
Colección:
01-internacional
Base de datos:
MEDLINE
Tipo de estudio:
Prognostic_studies
Idioma:
En
Revista:
J Chem Phys
Año:
2020
Tipo del documento:
Article
País de afiliación:
Estados Unidos