Rydberg, valence and mixed states in the vertical spectrum of HF

Abstract

Size-consistent self-consistent multireference singles and doubles configuration interaction (SC) 2–MR–SDCI, and linear response coupled cluster of singles and doubles including triples LR–CCSDR(3) methods, with a basis set of ANO’s augmented with a single series of molecular Rydberg functions, have been applied to the calculation of vertical excitation energies of HF in the 10–16 eV region. Special care has been put in the description of the valence, Rydberg and mixed states. Some advantage has been taken from the different physical contents of the methods to discuss some assignments. The (4,5) f Rydberg states of HF are predicted at 15.2 and 15.5 eV.