Abstract

Reactions of photochemical hydrogen transfer are modeled by means of quantum chemistry. Nitromethane and nitrobenzene in the triplet state in combination with ammonia, methylamine, or dimethylamine as hydrogen donors are studied. The structures of reaction complexes of the original materials, the transitional states and reaction products, the activation energies of the reactions, and changes in the standard enthalpies of the reactions are determined. The profiles of the potential energy surfaces of certain reactions are modeled. It is established that all profiles are very smooth, and the activation energies are low. The distribution of electron density in complexes is studied using Bader’s theory of atoms in molecules. All complexes have a characteristic ring structure that can be considered a source of additional interaction during a reaction. It is suggested that such a structure is responsible for the low activation energies of the reaction.

中文翻译：

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三重态的脂肪族和芳香族硝基化合物对胺的反应性

摘要

光化学氢转移反应是通过量子化学建模的。研究了三重态的硝基甲烷和硝基苯与氨，甲胺或二甲胺作为氢供体的组合。确定了原始材料的反应配合物的结构，过渡态和反应产物，反应的活化能以及反应的标准焓的变化。对某些反应的势能面的分布进行了建模。可以确定的是，所有轮廓都很平滑，活化能很低。使用巴德尔分子中的原子理论研究了配合物中电子密度的分布。所有配合物均具有特征性的环结构，可以认为是反应过程中其他相互作用的来源。