Vibrational mode-selective chemistry: Methane dissociation on Ni(100)

A first-principles full-dimensional model for CH4 dissociation on Ni(100) is derived using a reaction path formulation. Vibrational excitation of the methane is found to significantly enhance reactivity when the molecule undergoes transitions to the ground or lower-energy vibrational states with the excess energy converted into motion along the reaction path. The nu(1) vibration has the largest efficacy for promoting reaction, with the nu(3) efficacy smaller, but significant.