Three-dimensional analytical model for the photodissociation of symmetric triatomics. Absorption and fluorescence spectra of ozone

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Abstract
A full three‐dimensional analytical Franck–Condon analysis is presented for dissociative spectroscopies of a symmetric triatomic system. Formulas derived for harmonic potential surfaces are applied to the theoretical calculation of ozone absorption spectrum in the Hartley continuum as well as to the determination of its fluorescence (or resonance Raman) spectrum when submitted to 266 nm wavelength excitation. The Hartley absorption line shape describing the 1 1B2←X 1A1 photodissociation is reproduced within very good agreement with experiment. The role of the so‐called Duschinsky effect originating from the coupling of bending and stretching motions in the excited state is analyzed and comparisons are presented with previous more simple models neglecting this coupling. The influence of temperature is also taken into account through calculations dealing with vibrationally excited species. As for the photoemission fluorescence spectrum carrying a rich information content, the behavior is successfully predicted in its main lines, relative intensities of overtone progressions and of combination bands are fairly well reproduced.