Fluctuations in absorption spectra and final product state distributions following photodissociation processes.

We present a quantum mechanical wave packet study for the unimolecular dissociation of a triatomic molecule into an atom and a diatom. The 3D potential energy surface used in the dynamics calculations is that of the B state of water corresponding to the second absorption band. Both OH stretching coordinates and the bending angle are included. What is not taken into account is the strong nonadiabatic coupling to the lower-lying A and X states which in reality drastically shortens the lifetime in the B state. For this reason the present study is not a realistic account of the dissociation dynamics of water in the 122 nm band. It is, however, a representational investigation of a unimolecular reaction evolving on a realistic potential energy surface without barrier. The main focus is the resonance structure of the absorption spectrum and the final rotational state distributions of the OH fragment. The total absorption spectrum as well as the partial dissociation cross sections for individual rotational states of OH show drastic fluctuations caused by overlapping resonances. The widths of the individual resonances increase, on average, with the excess energy which has the consequence that the cross sections become gradually smoother. Although the low-energy part of the spectrum is rather irregular, it shows ‘‘clumps’’ of resonances with an uniform spacing of ∼0.1 eV. They are discussed in the context of IVR and a particular unstable periodic orbit. In accordance with the fluctuations in the partial dissociation cross sections as functions of the excess energy the final rotational state distributions show pronounced, randomlike fluctuations which are extremely sensitive on the energy.The average is given by the statistical limit (PST), in which all levels are populated with equal probability. With increasing excess energy the distributions more and more exhibit dynamical features which are reminiscent of direct dissociation like... [ABSTRACT FROM AUTHOR]