Electronic Wavefunction Tiles

We review the pre-quantum theories of electronic structure of Lewis and Langmuir, and how this relates to the post-quantum double-quartet theory of Linnett. Linnett’s ideas are put on a firm theoretical footing through the emergence of the wavefunction tile: The 3N-dimensional repeating structure of the N-electron wavefunction. Wavefunction tiles calculated by the dynamic Voronoi Metropolis sampling method are reviewed, and new results are presented for bent bonds of cyclopropane, and electron correlation in Be-O-Be.

Bent bonds (τ) and the antiperiplanar hypothesis, and the reactivity at the anomeric center in pyranosides

Hyperconjugation combined with the BBA hypothesis explainsC- andO-glycosylation of bicyclic pyranoside donors with an equatorial or axial C2–OBn group.

Bent bonds and the antiperiplanar hypothesis – a simple model to rationalize [1,3]-sigmatropic alkyl shifts

The stereochemical outcome of [1,3]-sigmatropic rearrangements can be rationalized by the use of olefinic tau (τ) bonds, and by considering that diradical intermediates have pyramidal character.