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The cavity ringdown spectrum of the visible electronic system of thiophosgene: An estimation of the lifetime of the T1(ã 3A2) triplet state
To obtain insights into the photophysical properties of collision-free T1(ã 3A2) thiophosgene, Cl2CS, the cavity ringdown (CRD) spectrum of the T1S0 absorption system was recorded under superso...
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The vibronically-resolved emission spectrum of disulfur monoxide (S2O): An algebraic calculation and quantitative interpretation of Franck–Condon transition intensities

J. Chem. Phys. 111, 5038 (1999); doi:10.1063/1.479786

Issue Date: 15 September 1999

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T. Müller and P. H. Vaccaro
Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107

F. Pérez-Bernal and F. Iachello
Center for Theoretical Physics, Yale University, New Haven, Connecticut 06520-8120
Emission spectra obtained from jet-cooled disulfur monoxide (S2O) molecules have been interpreted by means of a novel Lie algebraic formalism that makes possible the facile evaluation of multidimensional Franck–Condon factors. Fluorescence accompanying selective excitation of isolated vibronic bands in the S2O C-tilde 1A[prime] <-- X-tilde 1A[prime](pi* <-- pi) absorption system has been dispersed under moderate spectral resolution, allowing assignment of ground state levels possessing up to 20 quanta of vibration in the nu2 S–S stretching mode [Evib(X-tilde) <= 13 900 cm–1]. Aside from providing a rigorous and economical description for the inherently anharmonic nature of highly-excited polyatomic species, our algebraic approach enables quantitative information on molecular wavefunctions to be extracted directly from spectroscopic data. The emerging picture of S2O vibrational dynamics suggests that the X-tilde 1A[prime] potential surface is substantially more "local" in character than the C-tilde 1A[prime] manifold. While the observed pattern of X-tilde 1A[prime] vibrational energies could be reproduced well through use of model Hamiltonians that include only diagonal anharmonicities in the local algebraic basis, successful treatment of the C-tilde 1A[prime] state necessitated explicit incorporation of off-diagonal anharmonicities that lead to pervasive mixing of local vibrational character. This disparate behavior is manifest strongly in measured C-tilde–X-tilde transition strengths, thereby allowing detailed investigations of Franck–Condon intensities to discern the underlying dynamics. Structural parameters deduced from algebraic analyses are in good accord with previous predictions of the change in S2O geometry accompanying pi* <-- pi excitation. ©1999 American Institute of Physics.
History: Received 28 April 1999; accepted 18 June 1999
Permalink: http://link.aip.org/link/?JCPSA6/111/5038/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.70.Ca
    Molecular properties and interactions with photons Intensities and shapes of molecular spectral lines and bands Oscillator and band strengths, lifetimes, transition moments, and Franck–Condon factors
  • 33.50.Dq
    Molecular properties and interactions with photons Fluorescence and phosphorescence; radiationless transitions, quenching (intersystem crossing, internal conversion) Fluorescence and phosphorescence spectra
  • 33.20.Wr
    Molecular properties and interactions with photons Molecular spectra Vibronic, rovibronic, and rotation–electron-spin interactions
  • YEAR: 1999

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0021-9606 (print)   1089-7690 (online)
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