3p Orbitals, Bent Bonds, and the Electronic Spectrum of the P4 Molecule

作者：Robert R. Hart, M. B. Robin, N. A. Kuebler · 发表于：The Journal of Chemical Physics · 年份：1965 · DOI：10.1063/1.1695771 · 被引用次数：59 · 研究领域：Inorganic Fluorides and Related Compounds、Boron and Carbon Nanomaterials Research、Advanced Chemical Physics Studies

The electronic spectrum of P4 has been calculated in the SCF–CI approximation using a 3p atomic orbital (AO) basis. The calculated spectrum is in semiquantitative agreement with that observed in the region 4–9 eV, and this agreement is taken to support the original premise of a 3p AO basis. Earlier work by others suggested that a 3p basis necessarily leads to bent bonds and a bent-bond strain energy. Our calculation predicts that strong pi bonds are present in the molecule, and their presence leads to a resonance which, in turn, vitiates the concepts of ``bend bonds'' and ``strain energy'' in P4. An electron density map is also derived for the valence-shell electrons, and it shows that the regions of highest density are situated symmetrically above each of the triangular faces of the tetrahedral P4 molecule, and, that although arcs of charge are present in the molecule, they do not connect the phosphorus nuclei, as might be expected for bent bonds.