Dynamics of the collisional electron transfer and femtosecond photodissociation of NaI on ab initio electronic energy curves

Ab initio dynamics on more than one electronic state is reported for the NaI system. This requires both a method for computing the electronic energy curves and their coupling and a matched method for propagating the equations of motion for the atoms. The long-range electron transfer (a ‘harpoon’ process) requires a particularly accurate electronic computation and many configurations are employed in a novel method which combines the advantages of the molecular orbital and valence bond approaches. The computation is performed ‘on the fly’ with the required electronic input being generated at each nuclear separation reached the system.