Many-body dispersion effects in the binding of adsorbates on metal surfaces

Abstract

A correct description of electronic exchange and correlation effects for molecules in contact with extended (metal) surfaces is a challenging task for first-principles modeling. In this work we demonstrate the importance of collective van der Waals dispersion effects beyond the pairwise approximation for organic--inorganic systems on the example of atoms, molecules, and nanostructures adsorbed on metals. We use the recently developed many-body dispersion (MBD) approach in the context of density-functional theory [Phys. Rev. Lett. 108, 236402 (2012); J. Chem. Phys. 140, 18A508 (2014)] and assess its ability to correctly describe the binding of adsorbates on metal surfaces. We briefly review the MBD method and highlight its similarities to quantum-chemical approaches to electron correlation in a quasiparticle picture. In particular, we study the binding properties of xenon, 3,4,9,10-perylene-tetracarboxylic acid (PTCDA), and a graphene sheet adsorbed on the Ag(111) surface. Accounting for MBD effects we are able to describe changes in the anisotropic polarizability tensor, improve the description of adsorbate vibrations, and correctly capture the adsorbate--surface interaction screening. Comparison to other methods and experiment reveals that inclusion of MBD effects improves adsorption energies and geometries, by reducing the overbinding typically found in pairwise additive dispersion-correction approaches.

References in corpus (6)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
• Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory
• The random phase approximation applied to solids, molecules, and graphene-metal interfaces: From weak to strong binding regimes
• Range-separated density-functional theory with random phase approximation applied to noncovalent intermolecular interactions
• van der Waals density functionals built upon the electron-gas tradition: Facing the challenge of competing interactions
• Accurate Ground State Energies of Solids and Molecules from Time Dependent Density Functional Theory

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• Thermal and electronic fluctuations of flexible adsorbed molecules: Azobenzene on Ag(111)
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• libMBD: A general-purpose package for scalable quantum many-body dispersion calculations
• Faraday-cage screening reveals intrinsic aspects of the van der Waals attraction
• van der Waals-corrected Density Functional Theory simulation of adsorption processes on noble-metal surfaces: Xe on Ag(111), Au(111), and Cu(111)
• The role of the van der Waals interactions in the adsorption of anthracene and pentacene on the Ag(111) surface
• Reproducibility of Potential Energy Surfaces of Organic/Metal Interfaces on the Example of PTCDA on Ag(111)
• Structure and vibrational properties of the PTCDA/Ag(111) interface: Bilayer vs. monolayer
• Computational design of metal-supported molecular switches: Transient ion formation during light- and electron-induced isomerisation of azobenzene
• Coulomb Interactions between Dipolar Quantum Fluctuations in van der Waals Bound Molecules and Materials