ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
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 resonance enhancements they provide in mass resolved multiphoton ionization spectroscopy. We also report ab initio calculations which yield optimized energies, geometries, and vibrational frequencies for the ground states of PF2 and of the PF+2 ion. Energetic considerations, and the observation that the frequencies of the ν1' (symmetric stretch) and ν2' (bending) modes in these excited states closely parallel those of the ground state ion, lead us to conclude that all nine excited states are Rydberg states belonging to series that converge to the ground state ionization limit. Polarization analyses and band contour simulations allow us to identify the electronic symmetries of the first two of these newly identified states (2B1 and 2A1, respectively) and to provide an estimate of the excited state geometries [r(P–F)≈1.49 A(ring), (angle)F–P–F≈109°].
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.468429
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