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

J Chem Phys. 2008 Jul 7;129(1):014506. doi: 10.1063/1.2943315.


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 x 10(6) 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.