Vibrational and Rotational Mode Specificity in The Cl + H2O → HCl plus OH Reaction: A Quantum Dynamical Study
Vibrational and Rotational Mode Specificity in The Cl + H2O → HCl plus OH Reaction: A Quantum Dynamical Study
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DOI：
10.1021/acs.jpca.5b03740
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发表时间：
2015-06-18
影响因子：
2.9
通讯作者：
Guo, Hua
中科院分区：
文献类型：
--
作者：
Song, Hongwei;Guo, Hua
利用初始状态选择的切比雪夫实波包方法，研究了Cl + H2O -> HCl + OH反应在基于从头算的全局势能面上的振动和旋转模式特异性。在离心突然和/或j移近似下的全维量子动力学结果表明，该反应在H2O的拉伸模式激发下得到强烈增强，而在弯曲激发下仅微弱增强。另一方面，发现组合模式比单个激励的总和更能增强反应。此外，H2O反应物的旋转激发会轻微抑制反应活性。观察到的模式特异性与最近提出的突然向量投影模型的预测一致，该模型将反应物模式的促进作用归因于它们与过渡态反应坐标的耦合。
The vibrational and rotational mode specificity of the Cl + H2O -> HCl + OH reaction is studied on a recently constructed ab initio based global potential energy surface using an initial state selected Chebyshev real wave packet method. The full-dimensional-quantum dynamical results under the centrifugal sudden and/or J-shifting approximations indicate that this reaction is enhanced strongly by excitations of the stretching modes of the H2O reactant but only weakly by bending excitations. On the other hand, combination modes are found to enhance the reaction more than the sum of individual excitations. In addition, rotational excitation of the H2O reactant slightly inhibits the reactivity. The observed mode specificity is consistent with the predictions of the recently proposed Sudden Vector Projection model, which attributes the promotional effects of the reactant modes to their couplings with the reaction coordinate at the transition state.