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DFT Study for the Reduction of N 2 O( 1 Σ + ) with CO( 1 Σ + ) Catalyzed by Cr +
Author(s) -
Liu Fengxia,
Zhang Jianhui,
Hu Minzhe,
Wang Yongcheng,
Leng Yanli
Publication year - 2010
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.201090233
Subject(s) - chemistry , catalysis , organic chemistry
Abstract The mechanism of the reaction N 2 O( 1 Σ + )+CO( 1 Σ + )→N 2 ( 1 Σ)+CO 2 ( 1 Σ) catalyzed by Cr + has been investigated on sextet and quartet potential energy surfaces. The reactions are studied by using the UB3LYP density functional method and the standard 6‐311+G(2d) basis sets. The geometries for reactants, the transition states and the products are completely optimized. The result shows that the reaction proceeds in a two‐step manner, each mechanism are insertion‐elimination and rearrangement mechanism. The involved crossing between the two potential energy surfaces have been discussed by means of the intrinsic reaction coordinate (IRC) approach, and the crossing points (CPs) are located. The minimum energy crossing point (MECP) that we obtained by the mathematical algorithm proposed by Harvey et al . has been also employed. Then the action of frontier molecular orbitals in MECPs were illuminated briefly. Finally, O‐atom affinities (OA) testified that the argumentation is thermodynamically allowed.