RT Journal Article
T1 The vibronically-resolved emission spectrum of disulfur monoxide  S2O : an algebraic calculation and quantitative interpretation of Franck–Condon transition intensities
A1 Müller, T.
A1 Vaccaro, P. H.
A1 Pérez Bernal, Francisco
A1 Iachello, F.
AB Emission spectra obtained from jet-cooled disulfur monoxide (S2O) molecules have beeninterpreted by means of a novel Lie algebraic formalism that makes possible the facile evaluation ofmultidimensional Franck–Condon factors. Fluorescence accompanying selective excitation ofisolated vibronic bands in the S2O C˜ 1A8 X˜ 1A8(p* p) absorption system has been dispersedunder moderate spectral resolution, allowing assignment of ground state levels possessing up to 20quanta of vibration in the n 2 S–S stretching mode @Evib(X˜ )<13 900 cm21#. Aside from providinga rigorous and economical description for the inherently anharmonic nature of highly-excitedpolyatomic species, our algebraic approach enables quantitative information on molecularwavefunctions to be extracted directly from spectroscopic data. The emerging picture of S2Ovibrational dynamics suggests that the X˜ 1A8 potential surface is substantially more ‘‘local’’ incharacter than the C˜ 1A8 manifold. While the observed pattern of X˜ 1A8 vibrational energies couldbe reproduced well through use of model Hamiltonians that include only diagonal anharmonicitiesin the local algebraic basis, successful treatment of the C˜ 1A8 state necessitated explicitincorporation of off-diagonal anharmonicities that lead to pervasive mixing of local vibrationalcharacter. This disparate behavior is manifest strongly in measured C˜ –X˜ transition strengths,thereby allowing detailed investigations of Franck–Condon intensities to discern the underlyingdynamics. Structural parameters deduced from algebraic analyses are in good accord with previouspredictions of the change in S2O geometry accompanying p* p excitation.
PB American Institute of Physics
SN 0021-9606
SN 1089-7690 (electrónico)
YR 1999
FD 1999
LK http://hdl.handle.net/10272/8134
UL http://hdl.handle.net/10272/8134
LA eng
NO Müller, T., Vaccaro, P.H., Pérez Bernal, F., Iachello, F.: "The vibronically-resolved emission spectrum of disulfur monoxide  S2O  : an algebraic calculation and quantitative interpretation of Franck–Condon transition intensities". Journal of Chemical Physics. Vol. 111, n. 11, págs. 5038-5055 (1999). ISSN  0021-9606
DS Repositorio Institucional de la Universidad de Huelva
RD 1 jun 2026