Symmetry-Adapted Perturbation Theory Decomposition of the Reaction Force: Insights into Substituent Effects Involved in Hemiacetal Formation Mechanisms
Symmetry-Adapted Perturbation Theory Decomposition of the Reaction Force: Insights into Substituent Effects Involved in Hemiacetal Formation Mechanisms
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反作用力的对称自适应微扰理论分解：深入了解半缩醛形成机制中涉及的取代基效应
DOI：
10.1021/acs.jpca.9b06865
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Derricotte, Wallace D.
中科院分区：
文献类型：
--
作者：
Derricotte, Wallace D.
提出了基于对称适应摄动理论的反力分解方法。用该方法研究了CX3CHO(X=H，F，Cl和Br3)取代醛与甲醇形成半缩醛的反应配位途径上的取代基效应，提供了反应驱动力和反应阻滞力分量的定量评估.我们的结果强调了在涉及卤代醛的反应中更有利的静电和诱导效应的重要性，这些反应导致了较低的活化能垒。用对称适应微扰理论(F-SAPT)进一步解释了这些取代基效应。结果表明，该反应在很大程度上是由醛上的CX3基团和甲醇上的OH基团之间有利的直接非共价相互作用推动的。
The decomposition of the reaction force based on symmetry-adapted perturbation theory (SAPT) has been proposed. This approach was used to investigate the substituent effects along the reaction coordinate pathway for the hemiacetal formation mechanism between methanol and substituted aldehydes of the form CX3CHO (X = H, F, Cl, and Br), providing a quantitative evaluation of the reaction-driving and reaction-retarding force components. Our results highlight the importance of more favorable electrostatic and induction effects in the reactions involving halogenated aldehydes that leads to lower activation energy barriers. These substituent effects are further elucidated by applying the functional-group partition of symmetry-adapted perturbation theory (F-SAPT). The results show that the reaction is largely driven by favorable direct noncovalent interactions between the CX3group on the aldehyde and the OH group on methanol.