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Spectroscopy of the fluoromethylene radicals HCF and DCF by 2+1 resonance enhanced multiphoton ionization spectroscopy and by ab initio calculation

J. Chem. Phys. 103, 1303 (1995); doi:10.1063/1.469807

Issue Date: 22 July 1995

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Karl K. Irikura, Jeffrey W. Hudgens, and Russell D. Johnson III
Chemical Kinetics and Thermodynamics Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899
Spectra of fluoromethylene radicals, HCF and DCF, have been observed between 304 and 325 nm using mass-resolved, resonance enhanced multiphoton ionization (REMPI). Singlet HCF is generated by sequential reactions of atomic fluorine in either methane or methyl fluoride. The spectra arise from two-photon resonances between the ground state X-tilde 1A[prime] and the previously unobserved E-tilde 1A[prime] (3p) Rydberg state. The band origins lie at T0=62154±2 cm−1 (321.69±0.01 nm) and T0=62175±2 cm−1 (321.58±0.01 nm) (2sigma) above the ground states for HCF and DCF, respectively. Vibrational resolution and partial rotational resolution are obtained, with nu<sub>2</sub><sup>[prime]</sup>=1128±4 cm−1 and nu<sub>3</sub><sup>[prime]</sup>=1614±4 cm−1 for HCF and nu<sub>1</sub><sup>[prime]</sup>=2095±5 cm−1, nu<sub>2</sub><sup>[prime]</sup>=872±3 cm−1, and nu<sub>3</sub><sup>[prime]</sup>=1582±4 cm−1 for DCF (2sigma). Under typical experimental conditions, the strongest peak for HCF is due to the 2<sup>1</sup><sub>0</sub>3<sup>1</sup><sub>0</sub> resonance at 308.23±0.04 nm and the strongest peak for DCF is due to the 2<sup>2</sup><sub>0</sub> resonance at 312.85±0.01 nm. The results of vibrational and rotational analyses are consistent with predictions from ab initio calculations, which also yield the adiabatic ionization potential IPa=10.06±0.05 eV (2sigma). The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 21 March 1995; accepted 17 April 1995
Permalink: http://link.aip.org/link/?JCPSA6/103/1303/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.20.-t
    Molecular properties and interactions with photons Molecular spectra
  • 31.15.Ar
    Electronic structure of atoms, molecules and their ions: theory Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) Ab initio calculations
  • 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: 1995

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0021-9606 (print)   1089-7690 (online)
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