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A Molecular Perspective on the d-Band Model: Synergy Between Experiment and Theory

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Abstract

The d-band model of Hammer and Nørskov (Nature 376:238, 1995 [3]) relating adsorption energies to the d-band position, and the adsorption energies to barriers in catalytic reactions, has been extremely successful in predicting reactivities and catalysts. In the present contribution we review recent combined experimental and theoretical work on chemical bond-formation at surfaces. We focus on the adsorbate and how the adsorbate electronic structure can be rehybridized through mixing with unoccupied states to generate the radical state, real or virtual, that can then form electron pairs with the metal d-states, as described by the d-band model. We discuss five important bonding situations: (i) atomic radical, (ii) diatomics with unsaturated π-systems (Blyholder model), (iii) unsaturated hydrocarbons (Dewar–Chatt–Duncanson model), (iv) lone–pair interactions, and (v) saturated hydrocarbons (physisorption). Where the d-band model predicts trends along the series of transition metals, the present work provides intuitive tools for predicting trends among different adsorbates.

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Acknowledgments

We gratefully acknowledge all the people involved in the various projects on which this contribution is based. This work was supported by the U.S. Department of Energy, Basic Energy Sciences through the SUNCAT Center for Interface Science and Catalysis, the Stanford Synchrotron Radiation Lightsource, a national user facility operated by Stanford University on behalf of the U.S. Department of Energy, Office of Basic Energy Sciences and by the Swedish Research Council.

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Authors and Affiliations

  1. FYSIKUM, AlbaNova University Center, Stockholm University, 10691, Stockholm, Sweden

    Lars Gunnar Moody Pettersson

  2. SUNCAT Center for Interfacial Chemistry and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road MS31, Menlo Park, CA, 94025, USA

    Anders Nilsson

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  1. Lars Gunnar Moody Pettersson
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  2. Anders Nilsson
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Correspondence to Lars Gunnar Moody Pettersson.

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Pettersson, L.G.M., Nilsson, A. A Molecular Perspective on the d-Band Model: Synergy Between Experiment and Theory. Top Catal 57, 2–13 (2014). https://doi.org/10.1007/s11244-013-0157-4

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