Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 2011-10-13

Theoretical investigation for the cycle reaction of N2O (x1∑+) with CO (1∑+) catalyzed by IrO(n)+ (n = 1, 2) and utilizing the energy span model to study its kinetic information.

JingYan Nian, YongCheng Wang, WeiPeng Ma, DaFang Ji, CuiLan Wang, MaoJi La

Index: J. Phys. Chem. A 115(40) , 11023-32, (2011)

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Abstract

The mechanisms of the reactions between N(2)O and CO catalyzed by IrO(n)(+) (n = 1, 2) have been investigated using B3LYP and CCSD(T) levels of theory. Spin inversion among three reaction profiles corresponding to the quintet, triplet, and singlet multiplicities was discussed by using spin-orbit coupling (SOC) calculations. The probability of electron hopping in the vicinity of the (MECP) has been calculated by the Landau-Zener-type model. The single P(1)(ISC) and double P(2)(ISC) passes estimated at MECP1(#) (SOC = 198.61 cm(-1)) are approximately 0.11 and 0.20, respectively. Important analysis and explanations were done using molecular orbital theory and natural bonding orbital (NBO). The energetic span (δE) model coined by Kozuch was applied in this cycle. The turnover frequency (TOF)-determining transition state (TDTS) and TDI (TOF-determining intermediate) were confirmed. Finally, TOF(IrO(+))/TOF(IrO(2)(+)) = 0.38 at 298 K.