Photoabsorption and photoemission of ozone in the Hartley band

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Abstract
Theoretical calculations of ozone photoabsorption and photoemission in the Hartley band are presented. The potential energy surfaces of Sheppard and Walker [J. Chem. Phys. 7 8, 7191 (1983)] and of Barbe et al. [J. Mol. Spectrosc. 4 9, 171 (1974)] are used for the excited (1B2) and ground (1A1) states, respectively. In contrast with several recent studies, large amplitude motion in the symmetric and asymmetric stretch coordinates is explicitly included. Qualitative agreement is obtained with the experimental emission spectrum at 266 nm, although some discrepancies persists, using either the original Sheppard–Walker surface or various modifications thereof. Moreover, the calculations do not reproduce the experimentally observed structure atop the Hartley absorption band, eliminating some possibilities for the origin of this structure. The photofragmentation dynamics was computed by numerical integration of the time‐dependent Schrödinger equation on a two‐dimensional grid, and spectral observables were recovered via Fourier transform.