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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Direct Ab Initio Dynamics Study on a Gas Phase Microsolvated S_N2 Reaction of F~-(H_2O) with CH_3Cl
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Direct Ab Initio Dynamics Study on a Gas Phase Microsolvated S_N2 Reaction of F~-(H_2O) with CH_3Cl

机译：F〜-（H_2O）与CH_3Cl气相微溶剂化S_N2反应的直接从头动力学研究

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摘要

A microsolvated S_N2 reaction of F~-(H_2O) with CH_3Cl has been investigated by means of direct ab initio dynamics calculations in order to elucidate a detailed reaction mechanism. A full dimensional ab initio potential energy surface including all degrees of freedom was used in the dynamics calculations. Total energies and gradients were calculated at each time step. The vibrational phase of CH_3Cl was generated classically so as to take a temperature of 10 K. The dynamics calculations showed that three reaction channels are concerned with the reaction at a fixed collision energy (E_(coll) = 4.42 kcal/mol). These are expressed by F~- + CH_3Cl → CH_3F + Cl~- + H_2O (channel I), F~- + CH_3Cl → CH_3F + Cl~- (H_2O) (channel II), and F~- + CH_3Cl → CH_3F(H_2O) + Cl~- (channel III). Channel I is three-body dissociation of each product. In channels II and III, Cl~- and CH_3F, respectively, are solvated by a water molecule. It was found that the main reaction pathway is channels I and III, while channel II is significantly minor at E_(coll) = 4.42 kcal/mol. In all channels, the halogen exchange occurs rapidly with very short lifetimes of early and late complexes (i.e., the reaction proceeds via direct mechanism), which is similar to the nonsolvated reaction F~- + CH_3Cl. The preference of the reaction channels was discussed on the basis of theoretical results.
机译：为了阐明详细的反应机理，已经通过直接从头算动力学研究了F〜-（H_2O）与CH_3Cl的微溶剂化S_N2反应。动力学计算中使用了包括所有自由度的全尺寸从头算起的势能表面。在每个时间步长计算总能量和梯度。 CH_3Cl的振动相通常以10 K的温度生成。动力学计算表明，在固定碰撞能量（E_（coll）= 4.42 kcal / mol）下，三个反应通道与反应有关。它们由F〜-+ CH_3Cl→CH_3F + Cl〜-+ H_2O（通道I），F〜-+ CH_3Cl→CH_3F + Cl〜-（H_2O）（通道II）和F〜-+ CH_3Cl→CH_3F（ H_2O）+ Cl〜-（通道III）。通道I是每种产品的三体解离。在通道II和III中，Cl〜-和CH_3F分别被水分子溶剂化。发现主要反应途径是通道I和III，而通道II在E_（coll）= 4.42 kcal / mol时明显较小。在所有通道中，卤素交换迅速发生，并且早期和晚期络合物的​​寿命非常短（即，反应通过直接机理进行），这类似于非溶剂化反应F〜+ CH_3Cl。根据理论结果讨论了反应通道的偏好。

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