DOI: 10.1063/1.454030. A dynamical theory of unimolecular ionic dissociation reactions in polar solvents

A dynamical theory of unimolecular ionic dissociation reactions in polar solvents

10.1063/1.454030

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

A dynamical theory for the rates of unimolecular dissociations in polar solvents is constructed. Two classes of dissociation reactions, with dipolar and ionic transition states, are considered, and the theory is illustrated for a generalized continuum model water solvent. The rate of charge variation along the reaction coordinate is found to play a central role. Deviations from equilibrium solvation transition state theory predictions are found and discussed. Two nonequilibrium solvation regimes—nonadiabatic solvation and polarization caging—occur, and their appearance is connected to whether the solvated transition state has a reactant-like or product-like charge distribution.

Bibliography

Zichi, D. A., & Hynes, J. T. (1988). A dynamical theory of unimolecular ionic dissociation reactions in polar solvents. The Journal of Chemical Physics, 88(4), 2513â2525.

Authors 2

Dominic A. Zichi (first)
James T. Hynes (additional)

References 45 Referenced 45

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Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 9:19 a.m.)
Deposited	1 year, 6 months ago (Feb. 10, 2024, 2:30 a.m.)
Indexed	1 year, 6 months ago (Feb. 10, 2024, 9:27 a.m.)
Issued	37 years, 6 months ago (Feb. 15, 1988)
Published	37 years, 6 months ago (Feb. 15, 1988)
Published Print	37 years, 6 months ago (Feb. 15, 1988)

Funders 0

None

BibTeX

@article{Zichi_1988, title={A dynamical theory of unimolecular ionic dissociation reactions in polar solvents}, volume={88}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.454030}, DOI={10.1063/1.454030}, number={4}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Zichi, Dominic A. and Hynes, James T.}, year={1988}, month=feb, pages={2513–2525} }

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