On the gas-phase (n = 1, 2) catalyzed reduction of N2O by H2: A density functional study

The mechanisms of the reactions between N2O and H2 in the gas phase catalyzed by PtO n + (n = 1, 2) have been investigated using UB3LYP and CCSD(T) levels of theory. The potential energy surfaces, crossing points and corresponding minimum energy crossing points have been explored. The involved possibility of spin inversion processes of 4/2MECPs are discussed by spin–orbit coupling (SOC) calculations, then the probability values of the quartet ( P 1 ISC ) and doublet ( P 2 ISC ) are estimated using the Landau–Zener-type model, respectively. The energetic span (δE) model coined by Kozuch was applied in this cycle to obtain some kinetic information. Furthermore, the TDTSs and TDIs were confirmed by the AUTOF program. The calculations showed that the δEs are 158.8 and 115.6 kJ mol−1, and the TOFs are 8.8 × 10−16 and 3.9 × 10−8 s−1 for the title reaction catalyzed PtO+ and PtO 2 + cations at 298 K, respectively. To be compared with the PtO+, the PtO 2 + has good catalytic function for the reaction of N2O + H2 → N2 + H2O in the gas phase at the standard temperature.