Delocalization in Valence Bond-Hyperconjugation

摘要

We consider delocalization in small molecules. The valence bond technology allows an arbitrary division of the 1-electron space in strictly separate, but nonorthogonal, spaces. Allowing or obstructing orbital mixing between subspaces during the SCF procedure is associated with incorporating or eliminating the hyperconjugation effect. We show an example for tert-butyl and trimethylsilyl cations and radicals. For H, for which really extensive basis sets are feasible, we extend the basis so far that the delocalization or hyperconjugation effect has nearly disappeared.