Theoretical investigations of spin-orbit coupling and kinetics in reaction NO _2 with CO catalyzed by gas phase bare Ir ~+

摘要

The potential energy surface (PES) corresponding to the reaction NO _2(~2A _1) with CO(~1∑ ~+) catalyzed by Ir ~+ has been investigated by using density functional theory (DFT). Minimum energy crossing points (MECPs) on the potential energy surfaces are located by using the methods of Harvey et al. The possible spin inversion processes are discussed by means of spin-orbit coupling (SOC) calculations. As a result, the values of the SOC constants at ~(4/2)MECP1 and ~(5/3)MECP2 are 617 and 1187cm ~(-1), respectively. The latter is found to be the energetically favored channel. The energetic span (δE) model coined by Kozuch was applied in this cycle to obtain some kinetic information. The turnover frequency (TOF) determining transition state (TDTS) and TOF determining intermediate (TDI) were confirmed, and the TOF was calculated by the AUTOF program at different temperatures.