Electronic structure Linnett theory

In conclusion, the Boys localization procedure may be considered as the mathematification of the qualitative Lewis and Linnett theories. As pointed out, in this perspective a formal signification of the symbols used by these authors can be proposed these represent not localized electrons but centroids of charge of localized orbitals. Within this interpretation, the former theories agree much better with the ideas of quantum mechanics such as the wave character of electrons that prevents their localization. Moreover, the results obtained by the Boys procedure allow us to predict the Lewis and (or) Linnett structures of many chemical species without performing explicit calculations. For example, linear and bent 1,3-dipoles are described by the following general formulas ... 

Our LMO approach to the electronic structure and reactivity of chemical species allowed us not only to generalize the (Lewis and Linnett) theory of valence but also to determine the mechanism of a wide variety of organic reactions. 

Linnett s procedure may be viewed as a refinement of classical structural theory In Linnett s theory, the van t Hoff-Lewis tetrahedral model is applied twice, once to each set of spins, with the assumption that, owing to coulombic repulsions between electrons of opposite spin, there may be, in some instances, a relatively large degree of spatial anticoincidence between a system s two spin-sets. 

The results provided by Linnett s approach are more detailed than those of Lewis theory. Moreover, particularly in the case of unpaired electron species, they are in better agreement with spectroscopic and structural experimental data. 

It seems now that both Samuel and Wheland held the widespread opinion that valence-bond structures for diamagnetic molecules must only have electron-pair bonds. Samuel and Wheland had attempted to transform the molecular orbital configurations for N2 and NO so that they would obtain electron-pair bonds for N2O. But neither worker used the correct procedure to obtain valence-bond stractures from diatomic molecular orbital configurations with one or more singly-occupied anti-bonding molecular orbitals. The technique that should be used was developed by Linnett in 1956 , and then by Green and Liimett in 1960 °, and it has formed the primary Pauling 3-electron bond basis for the increased-valence theory we use in this book. When this theory is applied to the excited Nj and NO... 

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