Bond-selective control of a heterogeneously catalyzed reaction

Energy redistribution, including the many phonon- assisted and electronically assisted energy- exchange processes at a gas- metal interface, can hamper vibrationally mediated selectivity in chemical reactions. We establish that these limitations do not prevent bond- selective control of a heterogeneously catalyzed reaction. State- resolved gas- surface scattering measurements show that the nu(1) C-H stretch vibration in trideuteromethane ( CHD3) selectively activates C-H bond cleavage on a Ni( 111) surface. Isotope- resolved detection reveals a CD3: CHD2 product ratio > 30: 1, which contrasts with the 1: 3 ratio for an isoenergetic ensemble of CHD3 whose vibrations are statistically populated. Recent studies of vibrational energy redistribution in the gas and condensed phases suggest that other gas- surface reactions with similar vibrational energy flow dynamics might also be candidates for such bond- selective control.