Outer- and inner-valence ionization spectra of NH3, PH3, and AsH3: symmetry-adapted cluster configuration interaction general-R study

Outer- and inner-valence ionization spectra of group V hydrides, NH3, PH3, and AsH3 were studied by the symmetry-adapted-cluster configuration-interaction (SAC-CI) general-R method. Fine details of the experimental spectra of these hydrides were reproduced and the quantitative assignments of the peaks were proposed. The inner-valence satellites were classified into those including the valence or Rydberg excitations. For NH3, we interpreted the spectrum using the relative intensity and proposed some unresolved bands. For PH3, bands 2 and 3, for which different assignments have been proposed, were attributed to the A12 inner-valence satellites. A detailed inner-valence satellite spectrum of AsH3 is theoretically proposed.