Semiclassical analysis of rotational state distributions in the photolysis of triatomic molecules: Mapping of ground state wave function and potential anisotropy

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Abstract
We investigate the influence of final state interaction on rotational state distributions in the photolysis of (model) triatomic molecules. All calculations are performed within the infinite-order-sudden approximation (IOSA). We find distinct modal structures, which depend systematically on the parameters of the system such as anisotropy, energy, mass, etc. Most of the observations can be directly explained in the semiclassical limit of the IOSA. The key quantities are the classical excitation function and an amplitude, which represents the angular variation of the ground state wave function and the anisotropy of the excited state potential. Assuming hard core potentials analytical expressions for the excitation function can be derived which explain all the trends found in the numerical calculations. The observed structures are believed to exist whenever the dissociation process is impulsive and many rotational states are involved. They are closely related to rotational rainbows in normal scattering. We believe that recently reported experimental distributions for ICN at long laser wavelengths can be qualitatively explained by the structures investigated in this article.