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Resonance enhanced multiphoton ionization spectroscopy of the PF radical

J. Chem. Phys. 104, 2789 (1996); doi:10.1063/1.471102

Issue Date: 22 February 1996

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

J. W. Hudgens
Chemical Kinetics and Thermodynamics Division, Chemical Science and Technology Laboratory, National Institute of Standards and Technology, Gaithersburg, Maryland 20899
PF radicals in both their ground (X 3Sigma–) and metastable (a 1Delta) electronic states have been produced by the gas phase reaction of F atoms with phosphine in a discharge flow reactor and detected by mass selective resonance enhanced multiphoton ionization (REMPI) spectroscopy in the wavelength range 410–225 nm. Analysis of the longer wavelength end of this spectrum (lambda>~328 nm) has enabled identification and spectroscopic characterization of five hitherto unknown Rydberg states of this radical. These we label the h 1Sigma+ (T0=57 324.9 cm–1), D 3Delta (T0=58 223.0 cm–1), E 3Sigma– (T0=58 690 cm–1), i 1Delta (T0=59 881.6 cm–1), and j 1Sigma– (T0=61 873.9 cm–1) states, respectively. [Origins, relative to the lowest rovibrational level of the ground (X 3Sigma–) state are indicated by the numbers in brackets.] Quantum defect arguments suggest that all five states derive from the electronic configuration [2Pi]4ppi1. Within the shorter wavelength region we identify two additional sets of poorly resolved resonances which we associate with a further two Rydberg states belonging to series converging to the ground state ionization limit, followed by two extensive progressions of bands. Possible assignments for these two progressions are considered. ©1996 American Institute of Physics.
History: Received 21 September 1995; accepted 8 November 1995
Permalink: http://link.aip.org/link/?JCPSA6/104/2789/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.50.+w
    Electronic structure of atoms, molecules and their ions: theory Excited states
  • 33.80.Rv
    Molecular properties and interactions with photons Photon interactions with molecules Multiphoton ionization and excitation to highly excited states (e.g., Rydberg states)
  • YEAR: 1996

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ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (34)
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