Iron- and cobalt-exchanged ZSM-5 are active catalysts for the dissociation of nitrous oxide. In this study, density functional theory was used to assess a possible I reaction pathway for the catalytic dissociation of N2O. The active center was taken to be mononuclear [FeO](+) or [CoO](+), and the surrounding portion of the zeolite was represented by a 24-atom cluster. The first step of N2O decomposition involves the formation of [FeO2](+) Or [CoO2](+),and the release of N-2. The metal-oxo species produced in this step then reacts with N2O again, to release N-2 and O-2. The apparent activation energies for N2O dissociation in Fe-ZSM-5 and CoZSM-5 are 39.4 and 34.6 kcal/mol, respectively. The preexponential factor for the apparent first-order rate coefficient, is estimated to be of the order 107 s(-1) Pa1-. Although the calculated activation energy for FeZSM-5 is in good agreement with that measured experimentally, the value of the preexponential factor is an order of magnitude smaller than that observed. The calculated activation energy for Co-ZSM-5 is higher than that reported experimentally. However, consistent with experiment, the rate of N2O decomposition on Co-ZSM-5 is predicted to be significantly higher than that on Fe-ZSM-5.