Jd. Howe et al., OBSERVATION OF THE PF2 RADICAL BY RESONANCE-ENHANCED MULTIPHOTON IONIZATION SPECTROSCOPY, The Journal of chemical physics, 101(5), 1994, pp. 3549-3557
We have observed nine new excited electronic states of the PF2 radical
in the wave number range 50 000-71 000 cm(-1) via the two photon reso
nance enhancements they provide in mass resolved multiphoton ionizatio
n spectroscopy. We also report ab initio calculations which yield opti
mized energies, geometries, and vibrational frequencies for the ground
states of PF2 and of the PF2+ ion. Energetic considerations, and the
observation that the frequencies of the nu(1)' (symmetric stretch) and
nu(2)' (bending) modes in these excited states closely parallel those
of the ground state ion, lead us to conclude that all nine excited st
ates are Rydberg states belonging to series that converge to the groun
d state ionization limit. Polarization analyses and band contour simul
ations allow us to identify the electronic symmetries of the first two
of these newly identified states (B-2(1) and (2)A(1) respectively) an
d to provide an estimate of the excited state geometries [r(P-F)approx
imate to 1.49 Angstrom angle F-P approximate to 109 degrees].