AN EXAMINATION OF SUBSTITUENT EFFECTS ON THE REACTION OF OH RADICALS WITH HXCO (WHERE X = H, F, AND CL)

被引:54
作者
FRANCISCO, JS
机构
[1] Department of Chemistry, Wayne State University, Detroit
关键词
D O I
10.1063/1.462412
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
In the present work, ab initio molecular orbital theory have been used in the study of the reaction of OH radicals with HXCO (where X = H, F, and Cl). Equilibrium geometries and transition state structures have been fully optimized at the unrestricted Hartree-Fock (UHF)/6-31G*, unrestricted Moller-Plesset (UMP2)/6-31G* and UMP2/6-311G** levels of theory. Activation energy barriers and heats of reaction have been estimated using fourth-order Moller-Plesset perturbation theory with spin projection including single, double, triple, and quadruple excitations with extended basis sets. Transition state theory treatment of the kinetics of these reactions is performed and is used to estimate the rate coefficient at 299.3 K. The results for the OH + H2CO reaction show reasonable agreement with experiment.
引用
收藏
页码:7597 / 7602
页数:6
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