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

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

The reactions of N2O with H2 catalyzed by PtOn+ (n=1, 2). [Display omitted] •Theoretical study of the spin-forbidden reaction of N2O and H2 catalyzed by PtOn+ (n=1, 2).•Reactions are typical “two-state reactivity” (TSR) reactions, four crossing points are involved.•ISC takes place between high- and...

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Bibliographic Details
Published in:Computational and theoretical chemistry 2013-06, Vol.1013, p.78-84
Main Authors: Shi, Ning-Guo, Zhang, Jian-Hui, Wang, Yong-Cheng
Format: Article
Language:eng
Subjects:
[formula omitted] (n = 1, 2)
Minimum energy crossing point (MECP)
N2O and H2
Spin–orbit coupling (SOC)
TOF
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Summary:The reactions of N2O with H2 catalyzed by PtOn+ (n=1, 2). [Display omitted] •Theoretical study of the spin-forbidden reaction of N2O and H2 catalyzed by PtOn+ (n=1, 2).•Reactions are typical “two-state reactivity” (TSR) reactions, four crossing points are involved.•ISC takes place between high- and low-spin states with a large probability.•The energetic span (δE) model was applied in this cycle to obtain some kinetic information. The mechanisms of the reactions between N2O and H2 in the gas phase catalyzed by PtOn+ (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 (P1ISC) and doublet (P2ISC) 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 115.6kJmol−1, and the TOFs are 8.8×10−16 and 3.9×10−8s−1 for the title reaction catalyzed PtO+ and PtO2+ cations at 298K, respectively. To be compared with the PtO+, the PtO2+ has good catalytic function for the reaction of N2O+H2→N2+H2O in the gas phase at the standard temperature.
ISSN:2210-271X