Relative efficacy of vibrational vs. translational excitation in promoting atom-diatom reactivity: Rigorous examination of Polanyi's rules and proposition of sudden vector projection (SVP) model
Relative efficacy of vibrational vs. translational excitation in promoting atom-diatom reactivity: Rigorous examination of Polanyi's rules and proposition of sudden vector projection (SVP) model
复制标题
DOI：
10.1063/1.4810007
复制
发表时间：
2013-06-21
影响因子：
4.4
通讯作者：
Guo, Hua
中科院分区：
文献类型：
--
作者：
Jiang, Bin;Guo, Hua
为了系统和严格地重新检验著名的Polanyi规则，用切比雪夫实波包方法在精确的势能面上确定了几个A+BC(nu=0，1)反应的激发函数。讨论了具有早期(F+H-2和F+HCl)、晚期(Cl+H-2)和中心(H/D/Mu+H-2)势垒的反应，其中Mu是H的一种短寿命光同位素。尽管波兰尼规则与量子动力学结果大体上是一致的，但他们的预测仅在被交叉点划分的某些能量范围内严格有效。特别是，在高能时，双原子反应物的振动激发通常比平移激发更有效地提高反应性，而在低能时则相反。无论障碍物的位置如何，此功能都会持续存在。提出了一种替代Polanyi规则的突然矢量投影模型。研究发现，它对这些反应中的模式选择性给出了类似的、但更定量的预测，并且具有可扩展到涉及多原子分子的反应的优点。(C)2013 AIP出版有限责任公司。
To provide a systematic and rigorous re-examination of the well-known Polanyi's rules, excitation functions of several A + BC(nu = 0, 1) reactions are determined using the Chebyshev real wave packet method on accurate potential energy surfaces. Reactions with early (F + H-2 and F + HCl), late (Cl + H-2), and central (H/D/Mu + H-2, where Mu is a short-lived light isotope of H) barriers are represented. Although Polanyi's rules are in general consistent with the quantum dynamical results, their predictions are strictly valid only in certain energy ranges divided by a cross-over point. In particular, vibrational excitation of the diatomic reactant typically enhances reactivity more effectively than translational excitation at high energies, while reverse is true at low energies. This feature persists irrespective of the barrier location. A sudden vector projection model is proposed as an alternative to Polanyi's rules. It is found to give similar, but more quantitative, predictions about mode selectivity in these reactions, and has the advantage to be extendible to reactions involving polyatomic molecules. (C) 2013 AIP Publishing LLC.