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中文摘要：
双分子亲核（SN2）反应是重要的基本有机反应之一,其中电子从亲核基团向离去基团的转移发挥着关键作用.利用从头计算方法CCSD（T）/aug-cc-pVDZ和我们发展的分子形貌理论,对反应F-＋CH3Cl→CH3F＋Cl-进行了研究,给出了反应过程中分子形状和电子转移的动态变化图像.结果表明,沿内禀反应坐标,从反应开始到生成反应前复合物,亲核试剂F-的分子内禀特征轮廓在缓慢收缩,而其上的电子密度在缓慢增大.此后,F的轮廓迅速膨胀,电子密度急剧下降,尤其是从过渡态到产物复合物的过程中.而在反应过程中,离去基团Cl的轮廓一直在收缩,其上的电子密度一直在增大.对反应过程中电子所受到作用势的研究表明,随着反应的进行,电子在F与C间受到的作用势逐渐降低,而在C与Cl间受到的作用势逐渐升高,清楚地展现反应过程中F与C间化学键生成和C与Cl间化学键断裂的动态过程.
英文摘要：
Bimolecular nucleophilic substitution（S N 2）reactions are among the fundamental organic reactions,in which electron transfer from the nucleophilic group to the leaving group plays an essential role.We use a high-level ab initio CCSD（T）/aug-cc-pVDZ method in conjunction with our previously-developed molecular face（MF）theory,to investigate the S N 2 reaction F-＋CH 3 Cl→CH 3 F＋Cl-.Dynamic representations of molecular shape evolution and electron transfer features throughout the reaction are vividly presented.It is found that along the intrinsic reaction coordinate（IRC）,from the beginning of the reaction to the prereaction complex,the molecular intrinsic characteristic contour（MICC）of the nucleophile（F-）contracts slowly,while the electron density on the MICC increases slowly.The MICC of F then expands quickly,and the electron density decreases sharply,especially from the transition state to the product complex.However,for the leaving group（Cl）,the MICC contracts,and the electron density increases all along the reaction.Investigations of the potential acting on an electron in a molecule（PAEM）show that,as the reaction progresses,the PAEM gradually decreases between fluorine and carbon,while it gradually increases between carbon and chlorine.This study enhances our understanding of the dynamic processes of bond-forming between F and C atoms and bond-breaking between C and Cl atoms.
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