First-principles extrapolation method for accurate CO adsorption energies on metal surfaces

By S. Mason, I. Grinberg, Andrew M. Rappe. 2003

166 citations recorded by the source corpus.

We show that a simple first-principles correction based on the difference between the singlet-triplet CO excitation energy values obtained by density-functional theory ~DFT! and high-level quantum chemistry methods yields accurate CO adsorption properties on a variety of metal surfaces. We demonstrate a linear relationship between the CO adsorption energy and the CO singlet-triplet splitting, similar to the linear dependence of CO adsorption energy on the energy of the CO 2p* orbital found recently @Kresse et al., Phys. Rev. B 68, 073401 ~2003!#. Converged DFT calculations underestimate the CO singlet-triplet excitation energy DES-T , whereas coupled-cluster and configuration-interaction ~CI! calculations reproduce the experimental DES-T . The dependence of Echem on DES-T is used to extrapolate Echem for the top, bridge, and hollow sites for the ~100! and ~111! surfaces of Pt, Rh, Pd, and Cu to the values that correspond to the coupled cluster and CI DES-T value. The correction reproduces experimental adsorption site preference for all cases and obtains Echem in excellent agreement with experimental results.

Subfields: Atomic and Molecular Physics, and Optics, Catalysis, Materials Chemistry

View Paper: https://www.semanticscholar.org/paper/cd439aee803477bd0e9264d1ed032515d02a70f1

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In Atomic and Molecular Physics, and Optics

In Catalysis

In Materials Chemistry

Citations in the corpus

CatMAP: A Software Package for Descriptor-Based Microkinetic Mapping of Catalytic Trends (2015, background): “In order to properly describe the energetics of CO adsorption it is necessary to correct for the known over-binding [40, 41].”