INVESTIGATION OF $PF_{2}$ BY REMPI SPECTROSCOPY AND AB INITIO CALCULATIONS.

Abstract

Nine new electronic states of $PF_{2}$ have been observed using Resonance Enhanced Multiphoton Ionization Spectroscopy (REMPI). The states are observed in the $50000 to 71000 cm^{-1}$ energy region by 2+1 REMPI. The similarity of the excited state vibrational frequencies to the vibrational frequencies of the ground state ion indicate the Rydberg nature of the excited states. Ab inito calculations have been performed on the ground states of the neutral and ion to determine vibrational frequencies and the ionization potential at the QCISD(T)/6-311+G(3df) level. The energies of the lowest excited states of each symmetry were obtained at the CASPT2(3,8)/ANO level. These predominantly valence states all reside below $50000 cm^{-1}$.