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Titolo:
The vibronically-resolved emission spectrum of disulfur monoxide (S2O): Analgebraic calculation and quantitative interpretation of Franck-Condon transition intensities
Autore:
Muller, T; Vaccaro, PH; Perez-Bernal, F; Iachello, F;
Indirizzi:
Yale Univ, Dept Chem, New Haven, CT 06520 USA Yale Univ New Haven CT USA 06520 Univ, Dept Chem, New Haven, CT 06520 USA Yale Univ, Ctr Theoret Phys, New Haven, CT 06520 USA Yale Univ New Haven CT USA 06520 tr Theoret Phys, New Haven, CT 06520 USA
Titolo Testata:
JOURNAL OF CHEMICAL PHYSICS
fascicolo: 11, volume: 111, anno: 1999,
pagine: 5038 - 5055
SICI:
0021-9606(19990915)111:11<5038:TVESOD>2.0.ZU;2-V
Fonte:
ISI
Lingua:
ENG
Soggetto:
ROTATION-VIBRATION-SPECTRA; ELECTRON-MOLECULE SCATTERING; ATOM-DIATOM REACTIONS; POLYATOMIC-MOLECULES; MORSE OSCILLATOR; DYNAMICAL SYMMETRY; BENDING VIBRATIONS; CHEMICAL-REACTIONS; COMPLEX-MOLECULES; EIKONAL APPROACH;
Tipo documento:
Review
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
130
Recensione:
Indirizzi per estratti:
Indirizzo: Muller, T Yale Univ, Dept Chem, 225 Prospect St, New Haven, CT 06520 USA Yale Univ 225 Prospect St New Haven CT USA 06520 n, CT 06520 USA
Citazione:
T. Muller et al., "The vibronically-resolved emission spectrum of disulfur monoxide (S2O): Analgebraic calculation and quantitative interpretation of Franck-Condon transition intensities", J CHEM PHYS, 111(11), 1999, pp. 5038-5055

Abstract

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) over tilde (1)A(')<--(X) over tilde (1)A(')(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 nu(2) S-S stretching mode [E-vib((X) over tilde)less than or equal to 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 (1)A(') potentialsurface is substantially more "local" in character than the C (1)A(') manifold. While the observed pattern of X (1)A(') vibrational energies could bereproduced well through use of model Hamiltonians that include only diagonal anharmonicities in the local algebraic basis, successful treatment of the C (1)A(') 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-X transition strengths, thereby allowing detailed investigations of Franck-Condon intensitiesto 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. (C) 1999 American Institute of Physics. [S0021-9606(99)00635-2].

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Documento generato il 24/10/20 alle ore 11:21:35