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Reactions of atomic oxygen with complexes containing HCl are investigated and the OH product state distributions are compared to those observed for the corresponding reactions of HCl monomers. In previous studies of reactions of O(3P) with HCl and hydrocarbon complexes, rotationally colder OH product state distributions were observed, when compared to the corresponding reactions of monomers. In contrast, we find that reactions of O(1D) with HCl clusters yield OH rotational distributions that are unaffected by the incorporation of HCl into a van der Waals complex. Quasiclassical trajectories are run on collisions of oxygen with HCl and Ar⋯HCl at 1 eV collision energies to investigate the differences in the dynamics of the O(1D) and O(3P) reactions. It is found that when the van der Waals complex is longer lived than the collision complex, rotational and vibrational cooling are observed. In contrast, when the dissociation of the van der Waals complex is prompt, compared to the collision complex lifetime, the effects of complex formation on the internal energy of the OH product become negligible.


Originally published in the Journal of Chemical Physics 1998, 108, 9651-9657

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