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The photodissociation dynamics of some alkali halides are explored via the method of femtosecond transition-state spectroscopy (FTS). The alkali halide dissociation reaction is influenced by the interaction between the covalent and the ground state ionic potential energy surfaces (PES), which cross at a certain internuclear separation. Depending upon the adiabaticity of the PES, the dissociating fragments may be trapped in a well formed by the avoided crossing of these surfaces. Here, we detail the FTS results of this class of reactions, with particular focus on the reaction of sodium iodide: NaI*→[Na---I]°* →Na+I. As in our first report [T. S. Rose, M. J. Rosker, and A. H. Zewail, J. Chem. Phys. 88, 6672 (1988)], we observe the dynamical motion of the wave packet along the reaction coordinate and the crossing between the covalent and ionic surfaces. The studies presented here characterize the effects of various experimental parameters, including pump and probe wavelengths, on the dynamics of the dissociation and its detection. Comparisons of the results with classical and quantum mechanical calculations are also presented.

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