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 nu1 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.