Ring opening of dioxiranylmethyl radical: A caution on the use of G2-type ab initio MO methods for mechanistic analysis

被引:20
作者
Carpenter, BK [1 ]
机构
[1] Cornell Univ, Baker Lab, Dept Chem & Chem Biol, Ithaca, NY 14853 USA
关键词
D O I
10.1021/jp010797w
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
This letter reports the apparent failure of a nominally high-accuracy ab initio calculation of a modified G2 type for a reaction that is of considerable importance in hydrocarbon combustion. The failure is traced to the reliance on single-reference methods in the treatment of electron correlation. Its occurrence serves as a general caution about the use of such calculations for mechanistic analysis.
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页码:4585 / 4588
页数:4
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