Photodissociation and the Condon reflection principle

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Abstract
A semiclassical theory for photodissociation between separable potential energy surfaces, but with normal coordinate origin displacement and rotation, is derived by means of a Franck-Condon mapping between initial coordinate (Q 1, Q 2) and fragment energy (E vib, E trans) points. An algorithm for uniform Airy and uniform harmonic approximations is described. The latter expresses the transition amplitude in terms of the functional form of the initial, vibrational wavefunction, a direct realization of the Condon reflection principle. Test results for an exactly soluble model show agreement within 5 per cent and 1 per cent respectively for the uniform Airy and uniform harmonic model. An inversion procedure for the upper state potential, suggested by the structure of the theory, gives good results for the test model.