Theoretical investigations of the chemistry of singlet and triplet species. I. Insertion and abstraction reactions
Theoretical investigations of the chemistry of singlet and triplet species. I. Insertion and abstraction reactions
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单线态和三线态物质化学的理论研究。
DOI：
10.1021/ja00737a001
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发表时间：
1971
影响因子：
15
通讯作者：
R. Gangi
中科院分区：
文献类型：
--
作者：
R. Bader;R. Gangi
本文用SCF方法计算了0（3，））+2（'1+）模型体系的势能面，研究了单重态和三重态物种的不同插入和抽离倾向. O（3P）和O（1D）的化学差异与三重态氧的接近引起的衬底键中电子自旋的极化有关。对反应过程中未配对自旋空间分布的研究揭示了两种主要的自旋极化机制，一种是对应于在基底键的两个中心上具有相同自旋分量的电荷密度的局部化，以产生不稳定的三重态插入产物的未配对机制，
The differing tendencies of singlet and triplet species toward insertion and abstraction are investigated in an SCF calculation of the potential energy surfaces for the model system of 0 (3,))+ 2 ('1+) to yield eitherHiOLAO on insertion or(2)+ H (2S) on abstraction. The differences in chemistry of 0 (3P) and 0 (‘D) are related to a polarization of the electronic spins in the substrate bond induced by the approach of the triplet oxygen. Investigation of the spatial distribution of the unpaired spins during the course of the reaction reveals two principal mechanisms of spin polarization, an unpairing mechanism corresponding to the localization of charge density with identical spin components on both centers of the substrate bond to yield an unstable triplet insertion product and an