Adsorption of Benzene on Copper, Silver, and Gold Surfaces
MetadataShow full item record
Open access to this article available via the website of the American Chemical Society. http://acswebcontent.acs.org/home.html
The website for the Journal of Chemical Theory and Computation is available at:
The adsorption of benzene on the Cu(111), Ag(111), Au(111), and Cu(110) surfaces at low coverage is modeled using density-functional theory (DFT) using periodic-slab models of the surfaces as well as using both DFT and complete-active-space self-consistent field theory with second-order M-r-Plesset perturbation corrections (CASPT2) for the interaction of benzene with a Cu13 cluster model for the Cu(110) surface. For the binding to the (111) surfaces, key qualitative features of the results such as weak physisorption, the relative orientation of the adsorbate on the surface, and surface potential changes are in good agreement with experimental findings. Also, the binding to Cu(110) is predicted to be much stronger than that to Cu(111) and much weaker than that seen in previous calculations for Ni(110), as observed. However, a range of physisorptive-like and chemisorptive-like structures are found for benzene on Cu(110) that are roughly consistent with observed spectroscopic data, with these structures differing dramatically in geometry but trivially in energy. For all systems, the bonding is found to be purely dispersive in nature with minimal covalent character. As dispersive energies are reproduced very poorly by DFT, the calculated binding energies are found to dramatically underestimate the observed ones, while CASPT2 calculations indicate that there is no binding at the Hartree- Fock level and demonstrate that the expected intermolecular correlation (dispersive) energy is of the correct order to explain the experimental binding-energy data. DFT calculations performed for benzene on Cu(110) and for benzene on the model cluster indicate that this cluster is actually too reactive and provides a poor chemical model for the system.
Showing items related by title, author, creator and subject.
van der Waals corrected density functional calculations of the adsorption of benzene on the Cu (111) surfaceCarter, Damien; Rohl, Andrew (2014)We investigate the performance of several van der Waals (vdW) functionals at calculating the interactions between benzene and the copper (111) surface, using the local orbital approach in the SIESTA code. We demonstrate ...
Van der Waals corrected density functional calculations of the adsorption of benzene on the Cu (111) surfaceCarter, Damien; Rohl, Andrew (2014)© 2014 Wiley Periodicals, Inc.We investigate the performance of several van der Waals (vdW) functionals at calculating the interactions between benzene and the copper (111) surface, using the local orbital approach in the ...
Gandhi, Neha Sureshchandra (2011)Glycosaminoglycans (GAGs) are ubiquitous complex carbohydrate molecules present on the cell surfaces and in extracellular matrices (ECM) of vertebrate and invertebrate tissues. The interactions of sulphated GAGs such as ...