The weakly exothermic rearrangement of methoxy radical (CH3O⋅) to the hydroxymethyl radical (CH2OH⋅)
The weakly exothermic rearrangement of methoxy radical (CH3O⋅) to the hydroxymethyl radical (CH2OH⋅)
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DOI：
10.1063/1.444785
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发表时间：
1983-01
影响因子：
4.4
通讯作者：
S. Saebo;L. Radom;H. Schaefer
中科院分区：
文献类型：
--
作者：
S. Saebo;L. Radom;H. Schaefer
虽然CH 3 O和CH 2 OH自由基一直被认为是燃烧和大气过程中的关键中间体，但直到最近才认识到CH 3 O → CH 2 OH异构化的潜在意义。本文使用具有中等大基组并结合电子相关性的非经验分子电子结构理论研究了CH 3 O ⋅/CH 2 OH ⋅势面的这种异构化和相关方面。预测了CH 3 O、CH 2 OH和势能超曲面上其他七个驻点的振动频率，与光谱学的结果进行比较，并提供零点振动校正的估计。一般来说，有合理的协议，从实验中已知的那些振动频率的CH 3 O和CH 2 OH的。我们的从头计算预测，CH 3 O的能量比CH 2 OH的能量高5.0 kcal mol−1，重排为CH 2 OH的势垒为36.0 kcal mol−1。重新安排...
Although the CH3O⋅ and CH2OH⋅ radicals have long been considered critical intermediates in combustion and atmospheric processes, only very recently has the potential significance of the isomerization CH3O⋅→CH2OH⋅ been appreciated. This isomerization and related aspects of the CH3O⋅/CH2OH⋅ potential surface have been studied here using nonempirical molecular electronic structure theory with moderately large basis sets and with incorporation of electron correlation. The vibrational frequencies of CH3O⋅, CH2OH⋅ and seven other stationary points on the potential energy hypersurface have been predicted, both to compare with results from spectroscopy and to provide estimates of zero‐point vibrational corrections. In general, there is reasonable agreement with those vibrational frequencies of CH3O⋅ and CH2OH⋅ which are known from experiment. Our ab initio calculations predict that CH3O⋅ lies 5.0 kcal mol−1 higher in energy than CH2OH⋅ with a barrier to rearrangement to CH2OH⋅ of 36.0 kcal mol−1. Rearrangement of...