Previous results in our laboratory have demonstrated the effects of rovibrational excitation in the dissociative chemisorption of methane on Ni(100). In an effort to further probe the dynamics of this system, we have recently begun state-selected experiments of the molecule CD@sub 3@H on this surface. Replacing three hydrogen atoms with deuterium removes the spherical top symmetry and changes the nuclear motions of the normal modes. This gives us access to a nearly pure C-H stretching vibration (@nu@@sub 1@) and, by using polarized laser light, allows us to investigate the effects of the incident molecular orientation. This provides us with a method to more accurately probe the transition-state and may shed light on the role that dynamical steering plays in this reaction. In a related study, we have also been investigating the collision-induced absorption and collision-induced recombinative desorption of hydrogen on this surface. Our most recent results of these topics will be presented.