The Electronic Structures of the Group V Series ER3 (E = N→Sb; R=H, Hal). An Intercomparison of Photoelectron Spectra and SCC–Xα Calculations [1]

The He I photoelectron spectra o f the group V trihydrides and trihalides are assigned on the basis of a qualitative D3h/C3v-MO model which includes the analogous group III trihalides. Trends and irregularities across the series by varying either the central atoms or the substituents are discussed. U sing experimentally fitted (PES) and optimized parametrization the new SCC -Xα method yields results in excellent agreement with both measured ionisation potentials and dipole m om ents, especially for the heavier homologues. The electronic distribution and the trends in electronic and molecular properties are examined for the model series ER3 (E=N→Sb; R=H,Cl) and AsR′3(R′=H, Hal) within a complete SCC-Xα (and EHT) population analysis. - The PE Spectrum of BiMe3 is presented.