The H2 O2 +OH→ HO2 + H2 O reaction in aqueous solution from a charge-dependent continuum model of solvation

Bojana Ginovska, Donald M. Camaioni, Michel Dupuis

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

We applied our recently developed protocol of the conductorlike continuum model of solvation to describe the title reaction in aqueous solution. The model has the unique feature of the molecular cavity being dependent on the atomic charges in the solute and can be extended naturally to transition states and reaction pathways. It was used to calculate the reaction energetics and reaction rate in solution for the title reaction. The rate of reaction calculated using canonical variational transition state theory in the context of the equilibrium solvation path approximation, and including correction for tunneling through the small curvature approximation, was found to be 3.6× 106 M-1 s-1, significantly slower than in the gas phase in accord with experiment. These results suggest that the present protocol of the conductorlike continuum model of solvation with the charge-dependent cavity definition captures qualitatively and quantitatively the solvation effects at transition states and allows for quantitative estimates of reaction rates in solutions.

Original languageEnglish
Article number014506
JournalJournal of Chemical Physics
Volume129
Issue number1
DOIs
Publication statusPublished - 2008

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Solvation
solvation
continuums
aqueous solutions
Reaction rates
reaction kinetics
cavities
approximation
Gases
solutes
curvature
vapor phases
estimates
Experiments

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

The H2 O2 +OH→ HO2 + H2 O reaction in aqueous solution from a charge-dependent continuum model of solvation. / Ginovska, Bojana; Camaioni, Donald M.; Dupuis, Michel.

In: Journal of Chemical Physics, Vol. 129, No. 1, 014506, 2008.

Research output: Contribution to journalArticle

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