Rydberg states of the SH(SD) radical revealed by multiphoton ionization spectroscopy

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Abstract
Three hitherto uncharacterized Rydberg states of the SD radical, each arising from a … 5σ22π24p 1 ← … 5σ22π3 electronic promotion, have been identified through analysis of the rotationally structured two photon resonance enhancements each provides to the multiphoton ionization spectrum of this species. One, possessing 2Σ- symmetry, had actually been observed (but not recognized as such) in an earlier absorption study. The others, of 2Π and 2Φ symmetry, have not been reported previously. The SH radical was also observed to exhibit fragmentary rotational structure in the wavelength regions of the 2Σ--X 2Π and 2Φ-X 2Π transitions. The results provide strong support for the ab initio theoretical analysis of the vertical electronic spectrum of the mercapto radical by Bruna and Hirsch (1987, Molec. Phys., 61, 1359).
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