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Zusammenfassung:
Product state properties from the photodissociation of ozone in the ultraviolet Hartley band are investigated by trajectory surface-hopping calculations. The diabatic B and R state potential energy and coupling surfaces of Schinke and McBane [J. Chem. Phys. 132, 044305 (2010)] are employed. The properties computed include rotational and vibrational distributions in both the singlet and triplet channels, the total internal energy distribution in the triplet channel, and the photodissociation anisotropy parameter β in the singlet channel. A method for computing β from trajectories computed in internal Jacobi coordinates is described. In the singlet channel, the vibrational distribution is in good agreement with the experimental results. The observed increase in β with increasing photolysis wavelength is reproduced by the calculations and is attributed to the effects of the bending potential on the B state late in the fragmentation. The computed β values are too high with respect to experiment, and the peaks jmax of the singlet-channel rotational distributions are too low; these discrepancies are attributed to a too steep bending potential at long O-O distances. In the triplet channel, the main part of the internal energy distribution is described well by the calculations, although the detailed structures observed in the experiment are not reproduced. The experimental rotational distributions are well reproduced, although the maxima appear at slightly too high j. The triplet state product energy distributions are shown to depend largely on the distribution of hopping points onto the R state surface. A Landau-Zener model constructed as a function of the O2 bond distance provides a good physical description of the two-state dynamics. The high internal energy O2 products that cannot be attributed to the excitation of the Herzberg states remain unexplained.
