Apparent tunneling in chemical reactions

A necessary condition for tunneling in a chemical reaction is that the probability of crossing a barrier is non-zero, when the energy of the reactants is below the potential energy of the barrier. Due to the non-classical nature (i.e, momentum uncertainty) of vibrational states this is, however, not a sufficient condition in order to establish genuine tunneling as a result of quantum dynamics. This proposition is illustrated for a two-dimensional model potential describing dissociative sticking of N2 on Ru(s). It is suggested that the remarkable heavy atom tunneling, found in this system, is related to the high momentum tail of the initial vibrational state of nitrogen, allowing for amplitude to cross over the barrier.