Photodissociation and Half‐Collisions — Computational Viewpoint and Boundary Conditions

Boundary conditions and quantum mechanical numerical methods for evaluating transition probabilities of photodissociation and half‐collisional processes are presented. Direct and indirect dissociation modes are discussed. In each case we write a set of equations tying the particular boundary behaviour of each dissociation mode to the standard scattering boundary conditions. Numerical schemes based on these equations are presented. The case of competing dissociation reactions and exchange is also considered for the indirect case. When interference between these modes is expected to play a significant role, we show how the quantum jump due to photon and electron impact can be incorporated into the set of equations describing the dissociation. Finally we indicate how a numerical construction of potential surfaces from photofragment spectra and absorption spectra in the continuous and predissociation range can be obtained using these numerical schemes.