Reaction rates of the hydrated electron with N2O in high temperature water and potential surface of the N2O− anion

The reaction rate of hydrated electrons, (e−)aq, with N2O can be fitted with an Arrhenius-type temperature dependence up to 300 °C with an activation energy of 15.5 kJ/mol. At higher temperatures, the rate constant decreases to give a local minimum at 380 °C. Ab initio calculations of the N2O− anion suggest a possible dissociation path of N2O− in water. The calculated free energies for electron transfer suggest the (e−)aq reaction with N2O should fall on the ‘normal’ part of the Marcus parabola, and for this reason the reaction is not diffusion limited.