Resonance emission spectroscopy of predissociating SO{sub 2} {tilde C}(1thinsp{sup 1}B{sub 2}): Coupling with a repulsive {sup 1}A{sub 1} state near 200 nm

Journal Article · Thu Oct 01 04:00:00 EDT 1998 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.477139· OSTI ID:658472

Ray, P C; Arendt, M F; Butler, L J ^[1]

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1. The James Franck Institute and the Department of Chemistry, The University of Chicago, Chicago, Illinois 60637 (United States)

This work investigates the predissociative {tilde C}(1{sup 1}B{sub 2}) state of SO{sub 2} by cooling the SO{sub 2} in a pulsed molecular beam and dispersing the emission upon resonant excitation into several different vibronic absorption features in the {tilde C} state between 197 and 212 nm. Unlike at the lower excitation energies, the dispersed emission spectra at the higher excitation energies are dominated by progressions with odd quanta in the antisymmetric stretch mode {nu}{sub 3} and combination bands with up to six quanta in the bending mode {nu}{sub 2}. The formidable intensity for emission into vibrational states with odd quanta in the antisymmetric stretch of the jet-cooled molecule suggests that the intermediate state at high energies in the excited state is of mixed electronic character at nonsymmetric geometries, so the operative components of the transition moment for excitation and emission may be different. We discuss our results by considering the avoided crossing seam and coupling between the {tilde C}(1{sup 1}B{sub 2}) state and two dissociative states potentially involved in the electronic predissociation, the 3thinsp{sup 1}A{sub 1} and the 1thinsp{sup 3}A{sub 1} states. {copyright} {ital 1998 American Institute of Physics.}

• OSTI ID: 658472
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 13 Vol. 109; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

66 PHYSICS
ELECTRONIC STRUCTURE
EMISSION SPECTRA
EXCITED STATES
PREDISSOCIATION
SULFUR DIOXIDE
ULTRAVIOLET SPECTRA