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Observation of the PF2 radical by resonance enhanced multiphoton ionization spectroscopy

J. Chem. Phys. 101, 3549 (1994); doi:10.1063/1.468429

Issue Date: 1 September 1994

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J. D. Howe and M. N. R. Ashfold
School of Chemistry, University of Bristol, Bristol BS8 1TS, United Kingdom

J. W. Hudgens and R. D. Johnson III
Chemical Kinetics and Thermodynamics Division, Chemical Science and Technology Laboratory, National Institute of Standards and Technology, Gaithersburg, Maryland 20899
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<sup> + </sup><sub>2</sub> ion. Energetic considerations, and the observation that the frequencies of the nu<sub>1</sub><sup>[script ']</sup> (symmetric stretch) and nu<sub>2</sub><sup>[script ']</sup> (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)[approximately-equal-to]1.49 Å, [angle]F–P–F[approximately-equal-to]109°]. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 9 March 1994; accepted 17 May 1994
Permalink: http://link.aip.org/link/?JCPSA6/101/3549/1
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KEYWORDS and PACS

Keywords
PACS
  • 35.20.Wg
    Experimentally derived information on atoms and molecules; instrumentation and techniques Molecules Mass spectra
  • 33.80.Rv
    Molecular spectra and interactions of molecules with photons Photon interactions with molecules Multiphoton ionization and excitation to highly excited states (e.g., Rydberg states)
  • 33.10.Gx
    Molecular spectra and interactions of molecules with photons Calculation of molecular spectra Vibrational analysis
  • YEAR: 1994

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ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (27)
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