Dynamics of ion pair interconversion in a polar solvent

The reaction rate and mechanism of the interconversion between a contact ion pair and solvent separated ion pair in model polar solvents is investigated by molecular dynamics (MD) simulation. The full rate constant for the model reaction is estimated from the product of the transition state theory (...

Full description

Saved in:
Bibliographic Details
Published in:The Journal of chemical physics 1990-11, Vol.93 (10), p.7137-7147
Main Authors: CICCOTTI, G, FERRARIO, M, HYNES, J. T, KAPRAL, R
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
General and physical chemistry
Solutions
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The reaction rate and mechanism of the interconversion between a contact ion pair and solvent separated ion pair in model polar solvents is investigated by molecular dynamics (MD) simulation. The full rate constant for the model reaction is estimated from the product of the transition state theory (TST) rate constant, determined from the potential of mean force between the ions in an equilibrium solvent, and the transmission coefficient, which depends on the details of the dynamics. The collective character of the solvent motion in the reaction barrier crossing is examined in some detail, and the important role of solvent dynamics in causing the reaction rate to markedly deviate from the TST rate is discussed. The MD results are compared with the predictions of Kramers and Grote–Hynes theories.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.459437