Affiliation:
1. Department of Chemistry and W. M. Keck Foundation Laboratory for Materials Chemistry, Tufts University, Medford, MA 02155, USA.
Abstract
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 ν
1
C-H stretch vibration in trideuteromethane (CHD
3
) selectively activates C-H bond cleavage on a Ni(111) surface. Isotope-resolved detection reveals a CD
3
:CHD
2
product ratio > 30:1, which contrasts with the 1:3 ratio for an isoenergetic ensemble of CHD
3
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.
Publisher
American Association for the Advancement of Science (AAAS)
Cited by
198 articles.
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