ABINITIO MOLECULAR-ORBITAL STUDY OF ORGANIC-REACTIONS - ENERGY, CHARGE, AND SPIN DECOMPOSITION ANALYSES AT TRANSITION-STATE AND ALONG REACTION PATHWAY
ABINITIO MOLECULAR-ORBITAL STUDY OF ORGANIC-REACTIONS - ENERGY, CHARGE, AND SPIN DECOMPOSITION ANALYSES AT TRANSITION-STATE AND ALONG REACTION PATHWAY
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DOI：
10.1021/ja00474a005
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发表时间：
1978-01-01
影响因子：
15
通讯作者：
MOROKUMA, K
中科院分区：
文献类型：
--
作者：
NAGASE, S;MOROKUMA, K
摘要;从头算分子轨道计算已经进行了努力，以确定什么类型的化学相互作用发挥重要作用，以及如何有效地发生在过渡态和沿着反应途径的电荷和自旋重新分配。反应能垒表示为分子内形变能和分子间相互作用能之和，而分子间相互作用能又包括静电、极化、交换排斥、电荷转移以及它们的耦合项。分子内变形的重要性，特别强调在有关的有效的分子间相互作用。电荷转移相互作用在化学反应中起着比在电子给体-受体复合物和氢键等分子复合物中更重要的作用。此外，还发现随着反应离子性的增强，静电和极化相互作用变得显著。我们研究的具体反应体系是HCl、Cl ~+、CH_3 ~ 4、H ~+和H对烯烃的加成反应，涉及到CFG+ H、CH_4 + Cl和H_2 + 3 ~ 2的抽提反应，以及涉及到CH_4 + F ~-和CH_3F + F~-的取代反应。
Abstract; Ab initio molecular orbital calculations have been performed in an effort to determine what types of chemical inter-actions play essential roles, and how effectively the charge and spin redistributions occur at the transition state and along the reaction pathway. The reaction barrier is expressed as a sum of the intramolecular deformation energy and the intermolecular interaction energy, whichin turn consists of the electrostatic, polarization, exchange repulsion, charge transfer, and their cou-pling terms. The importance of the intramolecular deformation is especially emphasized in relation to the efficient intermolecular interaction. The charge transfer interaction plays a much more important role in chemical reactions than in molecular complexes such as electron donor-acceptor complexes and hydrogen bonds. Furthermore, it is found that the electrostatic and polarization interactionsbecome significant as the ionic character of the reaction is increased. The specific reaction systems we have investigated are the additions of HC1, Cl+, CHj4, H+, and H to olefins, the abstraction reactions involving CFG+ H, CH4+ Cl, and H2+ 3€ 2, and the substitution reactions involving CH4+ FI” and CH3F+ F~.