This paper illustrates the utility of combining high-quality electronic structure calculations, methods for determining reaction paths, and direct dynamics methods for studying nb initio trajectories on the fly to develop an understanding of complex chemical reactions. The combined methods are applied to the pseudorotation in SiH5-, competing dissociation paths for N2O2, the dissociation of FN3 into NF + N-2 and the potential energy surfaces for AlH2. These DRP results may be thought of as samples of what dynamical processes can be encountered on each potential energy surface.