Insight into the description of van der Waals forces for benzene adsorption on transition metal (111) surfaces

Abstract

Exploring the role of van der Waals (vdW) forces on the adsorption of molecules on extended metal surfaces has become possible in recent years thanks to exciting developments in density functional theory (DFT). Among these newly developed vdW-inclusive methods, interatomic vdW approaches that account for the nonlocal screening within the bulk [V. G. Ruiz, W. Liu, E. Zojer, M. Scheffler, and A. Tkatchenko, Phys. Rev. Lett. 108, 146103 (2012)] and improved nonlocal functionals [J. Klimes, D. R. Bowler, and A. Michaelides, J. Phys.: Condens. Matter 22, 022201(2010)] have emerged as promising candidates to account efficiently and accurately for the lack of long-range vdW forces in most popular DFT exchange-correlation functionals. Here we have used these two approaches to compute benzene adsorption on a range of close-packed (111) surfaces upon which it either physisorbs (Cu, Ag, and Au) or chemisorbs (Rh, Pd, Ir, and Pt). We have thoroughly compared the performance between the two classes of vdW-inclusive methods and when available compared the results obtained with experimental data. By examining the computed adsorption energies, equilibrium distances, and binding curves we conclude that both methods allow for an accurate treatment of adsorption at equilibrium adsorbate-substrate distances. To this end, explicit inclusion of electrodynamic screening in the interatomic vdW scheme and optimized exchange functionals in the case of nonlocal vdW density functionals is mandatory. Nevertheless, some discrepancies are found between these two classes of methods at large adsorbate-substrate separations.

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Cited by in corpus (7)

• van der Waals forces in density functional theory: The vdW-DF method
• van der Waals density functionals built upon the electron-gas tradition: Facing the challenge of competing interactions
• Adsorption energies of benzene on close packed transition metal surfaces using the random phase approximation
• The role of the van der Waals interactions in the adsorption of anthracene and pentacene on the Ag(111) surface
• Interface Characteristics at an Organic/Metal Junction: Pentacene on Cu Stepped Surfaces
• Selective Adsorption of a Supramolecular Structure on Flat and Stepped Gold Surfaces
• Density Functional study on the transesterification of triacetin assisted by cooperative weak interactions via a gold heterogeneous catalyst: Insights into Biodiesel production mechanisms