Theoretical Investigation for the Cycle Reaction of N sub(2)O (x super(1) capital sigma super(+)) with CO ( super(1) capital sigma super(+)) Catalyzed by IrO sub(n) super(+) (n = 1, 2) and Utilizing the Energy Span Model to Study Its Kinetic Information

The mechanisms of the reactions between N sub(2)O and CO catalyzed by IrO sub(n) super(+) (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...

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Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2011-01, Vol.115 (40), p.11023-11032-11023-11032
Main Authors: Nian, JingYan, Wang, YongCheng, Ma, WeiPeng, Ji, DaFang, Wang, CuiLan, La, MaoJi
Format: Article
Language:English
Subjects:
Bonding
Cobalt
Inversions
Mathematical models
Molecular orbitals
Nitrous oxides
Physical chemistry
Reaction kinetics
Online Access:Get full text
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Summary:The mechanisms of the reactions between N sub(2)O and CO catalyzed by IrO sub(n) super(+) (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 sub(1) super(ISC) and double P sub(2) super(ISC) passes estimated at MECP1 super(#) (SOC = 198.61 cm super(-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 ( delta E) 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 super(+))/TOF(IrO sub(2) super(+)) = 0.38 at 298 K.
ISSN:1089-5639
1520-5215
DOI:10.1021/jp202610u