SCF‐X αSW calculations on PH3 using a nonempirical scheme for choosing overlapping‐sphere radii

摘要: Detailed results of two SCF‐X αSW calculations on PH3, one with phosphorus d‐type partial waves (2) and without (1), are presented compared the best Hartree‐Fock calculations. Ionization energies for 5a1, 2e, 4a1 levels, respectively, 10.61, 13.42, 20.55 eV from 1 10.37, 13.60, 20.22 2, in better agreement experimental values 10.59 13.5 first levels than any previous first‐principles calculation. Total −342.6114 −342.6449 hartree respectively. Contour maps valence‐level wavefunctions total valence charge density presented; d functions found to contribute significantly (about 15%) only wavefunction 2e level, their effect being promote P–H overlap. Overlapping atomic sphere radii above were chosen by a nonempirical scheme involving satisfaction virial theorem relative sizes spheres around each atom which enclo...