Theoretical Reaction Dynamics Study of the Effect of Vibrational Excitation of CO on the OH + CO → H + CO2 Reaction†
Theoretical Reaction Dynamics Study of the Effect of Vibrational Excitation of CO on the OH + CO → H + CO2 Reaction†
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DOI：
10.1021/jp048855b
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发表时间：
2004-08
影响因子：
2.9
通讯作者：
Rosendo Valero;G. Kroes
中科院分区：
文献类型：
--
作者：
Rosendo Valero;G. Kroes
OH+CO、→、H+CO2反应是目前典型的形成络合物的四原子反应，近年来受到人们的广泛关注。一个有趣的问题是，非反应性CO键的振动在多大程度上充当了反应的旁观者。为了深入了解这个问题，我们报道了CO的基态(ν=0，j=0)和第一激发振动态(ν=1，j=0)与处于基振态(ν=0，j=0)的OH硅原子的反应性。对于这些反应，在总角动量J=0时，用含时波包(TDWP)方法在Bradley-Schatz势能面(PES)上计算了精确的全维(6D)初态选择反应几率。我们还使用了一个近似非绝热(势平均五维，PA5D)模型，其中6D势在一个渐近的CO振动波函数上取平均值。结果表明，CO的振动激发反应活性有较大幅度的提高。
The OH + CO → H + CO2 reaction has received a great deal of attention in recent years, being presently the prototypical complex-forming four-atom reaction. An interesting issue is the extent to which the vibration of the nonreactive CO bond acts as a spectator in the reaction. To get insight into this question, we report a study of the reactivity of the ground (ν = 0, j = 0) and first excited vibrational state (ν = 1, j = 0) of CO with the OH diatom in its ground rovibrational state (ν = 0, j = 0). For these reactions, the time-dependent wave packet (TDWP) method was used to calculate exact, full-dimensional (6D) initial-state selected reaction probabilities on the Bradley-Schatz potential energy surface (PES), for total angular momentum J = 0. An approximate diabatic (potential-averaged five-dimensional, PA5D) model was also used, in which the 6D potential is averaged over one asymptotic CO vibrational wave function. The results show a large increase in reactivity upon vibrational excitation of CO, parti...