Theoretical investigation into the Co+ catalytic activity in the cycle reaction of N2O with C2H6 in the gas phase

The spin-forbidden mechanism of the reaction between N2O and C2H6 catalyzed by Co+ has been investigated using UB3LYP density functional theory. The Harvey method has been applied-to optimize five minimum energy crossing points (MECP) on both triplet and quintet potential energy surfaces. Possible spin inversion processes are discussed by means of spin-orbit coupling calculations. According to the calculation of probability of electron hopping using the Landau-Zener formula, effective intersystem crossing may occur at each MECP. The energetic span model proposed by Kozuch has been applied to the catalytic cycles, and shows the turnover frequency teaches 3.35 x 10(-21) s(-1) when Co+ catalyzes the reaction to produce CH3CHO at 298K. (C) 2014, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.