New variational principles for photodissociation: L² amplitude density and scattered wave methods

In this paper we present two new formulations for the time-independent quantum mechanical calculation of photodissociation amplitudes. The first is based on a variational L² amplitude density approach, and the second is based on a new scattered wave variational principle, both approaches having been developed previously for the treatment of general reactive scattering problems. It is shown that, apart from an inhomogeneity term, the algebraic equations which must be solved are identical in form to those already successfully treated in recent three-dimensional, converged quantum reactive scattering studies. The new variational principles should provide a practical method for carrying out converged, three-dimensional quantal calculations for photodissociation processes in which any number of fragmentation pathways are possible.