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首页> 外文期刊>Physical chemistry chemical physics: PCCP >Bond and mode selectivity in the OH + NH2D reaction: a quasi-classical trajectory calculation
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Bond and mode selectivity in the OH + NH2D reaction: a quasi-classical trajectory calculation

机译：OH + NH2D反应中的键和模式选择性：准经典轨迹计算

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A state-to-state dynamics study was performed to analyze the effects of vibrational excitation on the dynamics of the OH + NH2D gas-phase reaction, which are connected to issues such as bond and mode selectivity. This reaction can evolve along two channels: H-abstraction, H2O(v) + NHD(v); and D-abstraction, HOD(v) + NH2(v). Based on an analytical potential energy surface previously developed by our group, quasi-classical trajectory calculations and subsequent normal mode analysis were performed. While vibrational excitation of the NH-sym mode of NH2D slightly favours H-abstraction over the D-abstraction, vibrational excitation of the ND mode shows that there is no clear preference for the H- or D-abstraction. These results show that this reaction does not exhibit bond selectivity, suggesting a breakdown of the spectator model. For H-abstraction, vibrational excitation of the non-reactive ND mode is partially retained in the NHD product; and for D-abstraction, excitation of the non-reactive NH mode is also partially retained in the products, indicating that this reaction exhibits mode selectivity only partially. In sum, we rule out bond and mode selectivity for this reaction. All these results were interpreted on the basis of strong coupling between modes along the reaction path, a behaviour which seems to be more the general tendency than the exception in polyatomic reactions.
机译：进行了状态间动力学研究，以分析振动激发对OH + NH2D气相反应动力学的影响，这与键和模式选择性等问题有关。该反应可以沿着两个途径发展：H-抽象，H2O（v）+ NHD（v）;和D-抽象，HOD（v）+ NH2（v）。基于我们小组先前开发的分析势能面，进行了准经典轨迹计算和随后的正态分析。尽管NH2D的NH-sym模式的振动激发比D-吸收略微有利于H-吸收，但是ND模式的振动激发表明，对于H-或D-吸收没有明显的偏好。这些结果表明该反应不表现出键选择性，表明观众模型的崩溃。对于H吸收，非反应性ND模式的振动激发被部分保留在NHD产品中。对于D-抽象，非反应性NH模式的激发也部分保留在产物中，表明该反应仅部分显示出模式选择性。总之，我们排除了该反应的键和模式选择性。所有这些结果都是基于沿着反应路径的模式之间的强耦合来解释的，这种行为似乎比多原子反应中的异常更普遍，而不是普遍的趋势。

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