摘要
The potential energy surface of the amino radical reaction with acetylene has been studied by the ab initio molecular orbital method, and the reaction rate has been computed by a multichannel RRKM calculation. At the highest G2M(RCC) level of theory, the barrier height for the addition step was calculated to be 8.24 kcal/mol, producing solely the HCCH-trans amino-vinyl radical. The adduct can further undergo NH2-for-H displacement decomposition and several isomerization reactions. The RRKM calculation was carried out for the lowest energy path, and the result indicates that the rate constant is expected to be pressure-dependent due to increased redissociation rate at low pressures. Kinetic modeling performed under experimental conditions reveals a substantial effect of secondary reactions on the observed NH2 decay rates. This may explain the low activation energies reported for this reaction.
原文 | English |
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頁(從 - 到) | 4687-4693 |
頁數 | 7 |
期刊 | Journal of Physical Chemistry A |
卷 | 102 |
發行號 | 24 |
DOIs | |
出版狀態 | Published - 11 6月 1998 |