We present the first application of first-principles molecular dynamics to a chemical process occurring on more than one electronic state. The example is the collisional chemi-ionization of NaI using a novel ab initio technique for the electronic states and a previously described full multiple spawning (FMS) classically motivated quantal method to describe the nuclear dynamics, The results for the dynamics are compared with fully exact quantal propagation, The FMS method which generates quantal amplitudes and inherently conserves normalization is shown to perform remarkably well for this heavy particle problem. The ab initio generated potentials and interstate couplings are compared with empirical potentials for NaI. Particular attention is given to the localized molecular orbital/generalized valence bond (LMO/GVB) method used for the electronic problem and to its interface with the equations of motion for the nuclei. The ability to incorporate atomic input (such as the ionization potential or the electron affinity) into the LMO/GVB method is emphasized.