Quantum Chemistry of Surface Chemical Reactivity

  • R. A. van Santen
Part of the NATO ASI Series book series (NSSB, volume 265)


The quantum chemist’s and surface physicist’s view of the surface chemical bond are illustrated by means of chemisorption of CO as an example. Between adsorbate and metal surface bonding as well as antibonding orbital fragments are formed. For molecules the adsorption geometry is a sensitive function of the balance of the repulsive atop directing interaction, resulting from the occupation of antibonding orbital fragments, and the high coordination directing bonding interaction. The bonding contribution to the surface chemical bond energy relates to the surface group orbital local density of states around the Fermi level, as long as the orbital interactions are weak. The concepts of Pauli repulsion and group orbital LDOS can be used to provide a quantum-chemical basis to metal promotion.


Fermi Level Potential Energy Curve Repulsive Part Pauli Repulsion Valence Electron Band 
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Copyright information

© Plenum Press, New York 1991

Authors and Affiliations

  • R. A. van Santen
    • 1
  1. 1.Schuit Institute of CatalysisUniversity of TechnologyEindhovenThe Netherlands

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