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The Electronic Spectrum of Gaseous CoO in the Visible Region

โœ Scribed by M. Barnes; D.J. Clouthier; P.G. Hajigeorgiou; G. Huang; C.T. Kingston; A.J. Merer; G.F. Metha; J.R.D. Peers; S.J. Rixon


Publisher
Elsevier Science
Year
1997
Tongue
English
Weight
796 KB
Volume
186
Category
Article
ISSN
0022-2852

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โœฆ Synopsis


Laser excitation spectra of gaseous CoO have been recorded using Doppler-limited intracavity spectroscopy and supersonic jet-cooled molecular beam methods. As seen in the molecular beam spectra there are nearly 100 bands arising from the X 4 D 7/2 spin component of the ground state in the wavelength region 430-720 nm. All of them are very strongly red-degraded and most of them are perturbed. 59 Co hyperfine broadenings or splittings have been observed in many. The bands can be arranged into five electronic transitions, together with a considerable number of ''extra'' bands induced by perturbations; two of the excited electronic states are 4 F, while the other three, which lie within 1700 cm 01 , are 4 D. Semi-empirical calculations have been carried out for the 4 D excited states, using exchange integrals transferred from the TiO and VO spectra; the predicted energies, spin-orbit structures, and relative intensities in absorption are consistent with the assignment of all three 4 D states to the same electron configuration, (4ss) 1 (3dd) 3 (3dp) 2 (3ds) 1 . It seems that there are extensive interactions between the excited 4 D states, because only one of them gives rise to a recognizable, though irregular, long vibrational progression in absorption. The other two progressions die out abruptly and unexpectedly after three or four members, presumably as a result of interference effects; however, wavelengthresolved fluorescence studies, together with calculations of the Franck-Condon overlap integrals to the various vibrational levels of the ground state, show that the upper state progressions reappear following a region of confused absorption. All of the excited states show highly irregular variations of their vibrational intervals and rotational constants with the vibrational quantum number, ยฃ. The wavelength-resolved fluorescence spectra give evidence for new low-lying electronic states of CoO at 3038, 5989, and 9105 cm 01 ; based on its vibrational frequency the 3038 cm 01 state is possibly the sd 4 p 2 B 4 S 0 state.


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