The reaction rate of hydrated electrons, (e(-))(aq), with N2O can be fitted with an Arrhenius-type temperature dependence up to 300 degreesC with an activation energy of 15.5 kJ/mol. At higher temperatures, the rate constant decreases to give a local minimum at 380 degreesC. 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. (C) 2003 Elsevier B.V. All rights reserved.