skip to main content

Title: The H2O2+OH → HO2+H2O reaction in aqueous solution from a charge-dependent continuum model of solvation

We applied our recently developed protocol of the conductor-like 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 CVT in the context of the equilibrium solvation path (ESP) approximation, and including correction for tunneling through the small curvature approximation (SCT) was found to be 3.6 106 M-1 s-1, in very good agreement with experiment, These results suggest that the present protocol of the conductor-like continuum model of solvation with the charge-dependent cavity definition captures accurately the solvation effects at transition states and allows for quantitative estimates of reaction rates in solutions. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.
Authors:
; ;
Publication Date:
OSTI Identifier:
949101
Report Number(s):
PNNL-SA-60053
Journal ID: ISSN 0021-9606; JCPSA6; KC0301020; TRN: US200907%%321
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics, 129(1):Article Number: 014506; Journal Volume: 129; Journal Issue: 1
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AQUEOUS SOLUTIONS; CHEMICAL REACTION KINETICS; SOLVATION; HYDROGEN PEROXIDE; HYDROXIDES; HYDROPEROXY RADICALS; WATER; MATHEMATICAL MODELS