The nature of multiple bonds. 1. .sigma.,.pi. Bonds versus bent bonds, a computational survey

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We examine the nature of multiple bonds within an independent-particle picture, climbing a hierarchy of approximations to the full generalized valence bond (GVB) description, the most general wave functions for which an independent particle interpretation of the bonding is possible. We begin with a systematic computational survey of molecules with multiple bonds, comparing σ,π and bent bond descriptions, using the strongly orthogonal perfect-pairing (SOPP) approximation to the GVB method. Although in several cases the bent-bond model is energeticaUy favored using SOPP-GVB wave functions, in a number of other cases the usually accepted σ,π bond description is energetically favored