Some aspects of orbital interactions through bonds: physical and chemical consequences
Some aspects of orbital interactions through bonds: physical and chemical consequences
复制标题
通过键进行轨道相互作用的某些方面：物理和化学后果
DOI：
10.1021/ar00080a003
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发表时间：
1982
影响因子：
18.3
通讯作者：
M. Paddon
中科院分区：
文献类型：
--
作者：
M. Paddon
1968年，霍夫曼、今村和黑尔报道了对双自由基体系的计算，这导致了现在经典的概念性解剖，将轨道相互作用分为通过空间和通过键的种类。1，2由于这个术语意味着通过空间的轨道相互作用是由两个相互作用的（基础）轨道的直接空间重叠引起的，&和&对于基础轨道之间重叠的正值，通过空间的相互作用总是导致轨道的成键组合（即，+50 b）在能量上低于反键组合（即，5- acfa）。这叫做自然轨道序列。[3]由于相互作用的程度[4]取决于基轨道之间重叠积分的大小[3]，因此，对于轨道间距大于3 π的情况，空间相互作用可以忽略不计。一、二
In 1968 Hoffmann, Imamura, and Hehre reported calculations on diradical systems that led to the now classic conceptual dissection of orbital interactions into through-space and through-bond varieties. 1, 2 As the term implies orbital interactions through space result from the direct, spatial overlap of two interacting (basis) orbitals, & and & For positive values of overlap between the basis orbitals, through space interactions always result in the bonding combination of orbitals (ie,+ 50b) lying below the antibonding combina-tion (ie, 5- acfa) in energy. This is called the natural sequence of orbitals. 3 Because the extent of the in-teraction4 depends on the size of theoverlap integral between the basis orbitals, 3 it follows that through-space interactions are negligible for interorbital separations greater than 3 Á. 1, 2