<br>OH− + CH3I 多通道反应动力学中的振动模式特异性,The Journal of Chemical Physics

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OH− + CH3I 多通道反应动力学中的振动模式特异性
The Journal of Chemical Physics ( IF 3.1 ) Pub Date : 2024-01-24 , DOI: 10.1063/5.0189561
Domonkos A Tasi ₁ , Gábor Czakó ₁

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我们报告了 OH− + CH3I 反应的振动模式特定动力学的全面表征。在我们之前开发的全维高水平从头算势能表面上以四种不同的碰撞能量进行准经典轨迹模拟，以检查反应物中四种不同的简正模式激发的影响。考虑到 OH− + CH3I 的 11 种可能途径，在反应性中观察到明显的模式特异性：一般来说，OH− 伸缩和 CH 伸缩的激发对通道的影响最大。对于 SN2 和质子抽象产物，反应物初始攻角和产物散射角分布没有显示出主要的模式特定特征，除了较高碰撞能量下的 SN2，其中 CI 拉伸和 CH 拉伸激发促进了前向散射。还检查了反应后能量流的 SN2 和质子提取，发现多余的振动激发能反而转移到产物振动能中，因为产物的平移和旋转能量分布不代表显着的模式特异性。此外，在质子提取过程中，由于直接剥离机制占主导地位，OH−反应物中的剩余振动能量大部分保留在H2O产物中。

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Vibrational mode-specificity in the dynamics of the OH− + CH3I multi-channel reaction

We report a comprehensive characterization of the vibrational mode-specific dynamics of the OH− + CH3I reaction. Quasi-classical trajectory simulations are performed at four different collision energies on our previously-developed full-dimensional high-level ab initio potential energy surface in order to examine the impact of four different normal-mode excitations in the reactants. Considering the 11 possible pathways of OH− + CH3I, pronounced mode-specificity is observed in reactivity: In general, the excitations of the OH− stretching and CH stretching exert the greatest influence on the channels. For the SN2 and proton-abstraction products, the reactant initial attack angle and the product scattering angle distributions do not show major mode-specific features, except for SN2 at higher collision energies, where forward scattering is promoted by the CI stretching and CH stretching excitations. The post-reaction energy flow is also examined for SN2 and proton abstraction, and it is unveiled that the excess vibrational excitation energies rather transfer into the product vibrational energy because the translational and rotational energy distributions of the products do not represent significant mode-specificity. Moreover, in the course of proton abstraction, the surplus vibrational energy in the OH− reactant mostly remains in the H2O product owing to the prevailing dominance of the direct stripping mechanism.

更新日期：2024-01-24

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