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Science 8 February 2008:
Vol. 319. no. 5864, pp. 790 - 793
DOI: 10.1126/science.1152819
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Reports

Bond-Selective Control of a Heterogeneously Catalyzed Reaction

Daniel R. Killelea,* Victoria L. Campbell, Nicholas S. Shuman,{dagger} Arthur L. Utz{ddagger}

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.

Department of Chemistry and W. M. Keck Foundation Laboratory for Materials Chemistry, Tufts University, Medford, MA 02155, USA.

* Present address: James Franck Institute, University of Chicago, Chicago, IL 60637, USA.

{dagger} Present address: Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599, USA.

{ddagger} To whom correspondence should be addressed. E-mail: arthur.utz{at}tufts.edu

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THIS ARTICLE HAS BEEN CITED BY OTHER ARTICLES:
Chemical Dynamics Special Feature: Chemical dynamics of vibrationally excited molecules: Controlling reactions in gases and on surfaces.
F. F. Crim (2008)
PNAS 105, 12654-12661
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Science. ISSN 0036-8075 (print), 1095-9203 (online)