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Bonding and Vibrational Properties of CO-Adsorbed Copper

Published online by Cambridge University Press:  10 February 2011

Steven P. Lewis  and
Andrew M. Rapp
Steven P. Lewis
Affiliation:
Department of Chemistry and Laboratory for Research on the Structure of Matter, University of Pennsylvania, Philadelphia, PA 19104.
Andrew M. Rapp
Affiliation:
Department of Chemistry and Laboratory for Research on the Structure of Matter, University of Pennsylvania, Philadelphia, PA 19104.
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Accurate density functional calculations are performed to investigate the structure and vibrational dynamics of carbon monoxide adsorbed to the (100) surface of copper. The adsorbate and substrate are considered as a unified system, with atoms of each treated on an equal footing. Coupling between the two components is found to have a significant effect. In particular, frustrated translational motion mixes strongly with transverse phonons of the substrate to form a broad resonance. Direct computation of anharmonic coupling between the internal CO bond stretching mode and other adsorbate-weighted modes confirms the experimental conclusion that the transient CO-stretch response seen in recent pump-probe studies is an indirect probe of the transient dynamics of frustrated translations. In this light, the computed resonance between this mode and substrate phonons suggests a dephasing mechanism to account for the observed relaxation dynamics.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 408: Symposium P – Materials Theory, Simulations, and Parallel Algorithms , 1995 , 391
Copyright
Copyright © Materials Research Society 1996

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