ALGEBRAIC APPROACH FOR THE CALCULATION OF POLYATOMIC FRANCK-CONDON FACTORS - APPLICATION TO THE VIBRONICALLY RESOLVED EMISSION-SPECTRUM OF S2O

Emission spectra obtained from jet-cooled disulfur monoxide (S2O) mole cules have been interpreted quantitatively by means of a U(2) Lie alge braic theory. Fluorescence accompanying selective excitation of the S2 O (C) over tilde (1)A' <-- (X) over tilde (1)A' (pi <-- pi) absorptio n system was dispersed under modest resolution, thereby permitting vib rational assignment of ground-state levels possessing up to 20 quanta of the nu(2) S-S stretching mode. Aside from providing a convenient fr amework for analysis of recorded energy patterns, the algebraic treatm ent allows for straightforward calculation of multidimensional Franck- Condon factors and corresponding transition intensities. The emerging picture of S2O vibrational dynamics suggests that the (X) over tilde ( 1)A' potential surface is substantially more 'local' in character than the (C) over tilde (1)A' manifold. (C) 1998 Elsevier Science B.V. All rights reserved.