State-to-state vibrational predissociation of H2–HF and D2–HF. Direct comparisons between theory and experiment

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Abstract
The optothermal detection method has been used to measure photofragment angular distributions resulting from the vibrational predissociation of both H2–HF and D2–HF. These angular distributions show resolvable structure which can be related to the final rotational state distributions, including the scalar intermolecular rotational correlations. H2–HF dissociates via a predominantly V–R process, while in D2–HF the open D2 vibrational channel is the main depository for the excess energy. The experimental results are compared directly with the recent time-independent close-coupling calculations of Clary [J. Chem. Phys. 96, 90 (1992)] and the time-dependent golden rule calculations of Zhang, Zhang, and Bačić [J. Chem. Phys. 97, 927; 3149 (1992); Chem. Phys. Lett. 194, 313 (1992)]. The fact that these two systems have very different dynamics, while the potential-energy surfaces are the same, is particularly useful in providing new insights into the nature of the coupling responsible for predissociation.

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