Rydberg - valence interactions of CO , and spectroscopic evidence characterizing the C 8 1 S ¿ valence state
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چکیده
Rotationally cold absorption and two-photon ionization spectra of CO in the 90–100 nm region have been recorded at a resolution of 0.3–1.0 cm. The analyses of up to four isotopomers seek to clarify the observations in regions where the Rydberg levels built on the ground state X S of the ion interact with valence states of S and P symmetry. Previous observations of the 3ss , B S Rydberg state, reviewed by Tchang-Brillet et al. @J. Chem. Phys. 96, 6735 ~1992!#, have been extended to energies above its avoided crossing with the repulsive part of the D8 S valence state where resonances of varying intensities and widths have been attributed to the fully coupled 3ss or 4ss and D8 potentials, and where the B state approaches a second avoided crossing with the C8 S valence state @Cooper and Kirby, J. Chem. Phys. 87, 424 ~1987!; 90, 4895 ~1989!; Chem. Phys. Lett. 152, 393 ~1988!#. Fragments of a progression of weak and mostly diffuse bands, observed for all four isotopomers, have been assigned to the C8←X transition. The least-squares modeling of the 4p and 5p complexes reveals the 3pp , E P Rydberg state to be one of the perturbers, violating the Dv50 selection rule for Rydberg–Rydberg interactions on account of its rapid transition with increasing v from Rydberg to valence state. A second P perturber, very loosely bound and clearly of valence type, contributes to the confusion in the published literature surrounding the 5p , v50 complex. © 2004 American Institute of Physics. @DOI: 10.1063/1.1756579#
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Rydberg-valence interactions of CO, and spectroscopic evidence characterizing the C' 1Sigma+ valence state.
Rotationally cold absorption and two-photon ionization spectra of CO in the 90-100 nm region have been recorded at a resolution of 0.3-1.0 cm(-1). The analyses of up to four isotopomers seek to clarify the observations in regions where the Rydberg levels built on the ground state X (2)Sigma(+) of the ion interact with valence states of (1)Sigma(+) and (1)Pi symmetry. Previous observations of th...
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تاریخ انتشار 2004