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Observation of NO B 2Pi(v=3)<--X 2Pi(v=0) absorptions with 1+1 multiphoton ionization: Precision line position measurements and parity assignment of the B 2Pi state
Absorptions are observed in the (3,0) band of NO, B 2(v=3)X 2(v=0) using 1+1 multiphoton ionization at photon energies in the range 47 801–48 542 cm−1. Line positions are reported in 10 of...

Triplet Rydberg states of the imidogen radical characterized via two-photon resonance-enhanced multiphoton ionization spectroscopy

J. Chem. Phys. 97, 7064 (1992); doi:10.1063/1.463532

Issue Date: 15 November 1992

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Simon G. Clement, Michael N. R. Ashfold, and Colin M. Western
School of Chemistry, University of Bristol, Bristol BS8 1TS, United Kingdom

Russell D. Johnson III and Jeffrey W. Hudgens
Chemical Kinetics and Thermodynamics Division, Chemical Science and Technology Laboratory, National Institute of Standards and Technology, Gaithersburg, Maryland 20899
Five new triplet excited states of the ND radical (three in the case of NH) in the wave-number range 85 000–91 000 cm−1 have been identified through analysis of the two-photon resonance enhancements they provide to the wavelength-resolved multiphoton ionization spectrum of X 3Sigma− state NH(ND) radicals. The lowest energy of these, the B 3Pi state, is found to be a ``regular'' Rydberg state which, on the basis of its observed quantum defect and its deduced rotational and spin–orbit coupling constant, is surmised to be the 3Pi state derived from a 3psigma electron built on the 2Pi ground-state ion core. Perturbations are evident in the B 3Pi–X 3Sigma− origin bands of both NH and ND. In the case of ND the perturbing state provides its own resonance enhancements, the analysis of which enables its definitive identification as the C 3Sigma− state. The very small spin–orbit splitting found for the D 3Pi state is taken to indicate that (at least in the Franck–Condon region) its wave function is dominated by the configuration involving one 3ppi Rydberg electron and a 4Sigma− ion core. To still higher wave number we identify two more 3Sigma− excited states, the upper of which (the F 3Sigma− state) has a very small rotational constant which we take to imply that it has substantial valence character. Further indications that the F 3Sigma− (and C 3Sigma−) states possess significant valence character is provided by the observation that both parent and daughter (N+) ions contribute to the overall ion yield when the multiphoton ionization proceeds via these two states. Daughter-ion formation is considered to occur via an overall four-photon excitation process in which the coherent two-photon excitation to the 3Sigma− state of interest is followed by a one-photon excitation to a ``superexcited'' state of the neutral. This is then presumed to absorb a further photon to yield the observed N+ ions and/or to predissociate, yielding highly excited N* atoms which then undergo a direct one-photon ionization. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 17 June 1992; accepted 4 August 1992
Permalink: http://link.aip.org/link/?JCPSA6/97/7064/1
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KEYWORDS and PACS

Keywords
PACS
  • 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)
  • 33.60.-q
    Molecular spectra and interactions of molecules with photons Photoelectron spectra
  • YEAR: 1992

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