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Ab initio calculations for the N( 2 D) + CH 4 reaction: Does the N( 2 D) atom really insert into CH bonds of alkane molecules?
Author(s) -
Takayanagi Toshiyuki,
Kurosaki Yuzuru,
Yokoyama Keiichi
Publication year - 2000
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/1097-461x(2000)79:3<190::aid-qua4>3.0.co;2-0
Subject(s) - chemistry , insertion reaction , complete active space , potential energy surface , alkane , ab initio , atom (system on chip) , atomic physics , energy profile , configuration interaction , ab initio quantum chemistry methods , potential energy , molecule , computational chemistry , molecular physics , density functional theory , energy (signal processing) , physics , basis set , hydrocarbon , quantum mechanics , catalysis , biochemistry , organic chemistry , computer science , embedded system
The geometry of the transition state for the N( 2 D) + CH 4 reaction has been reoptimized at the complete‐active‐space self‐consistent field theory with a large active space and we have confirmed that the N( 2 D) atom initially inserts into a CH bond to form adiabatically an intermediate radical, CH 3 NH( 2 A″). Extensive single‐point calculations at the multireference configuration interaction level of theory have also been carried out to understand the feature of the potential energy surface for the C–H insertion reaction. In addition, we have found that the N( 2 D)+CH 4 reaction dynamics on the second lowest doublet state ( 2 A′) is dominated by C–H insertion although the barrier height is somewhat larger in energy than the corresponding insertion barrier associated with the lowest doublet state. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 79: 190–197, 2000