Random phase approximation applied to solids, molecules, and graphene-metal interfaces: From van der Waals to covalent bonding

Thomas Olsen and Kristian S. Thygesen
Phys. Rev. B 87, 075111 – Published 13 February 2013

Abstract

The random phase approximation (RPA) is attracting renewed interest as a universal and accurate method for first-principles total energy calculations. The RPA naturally accounts for long-range dispersive forces without compromising accuracy for short-range interactions making the RPA superior to semilocal and hybrid functionals in systems dominated by weak van der Waals or mixed covalent-dispersive interactions. In this work, we present plane-wave-based RPA calculations for a broad collection of systems with bond types ranging from strong covalent to van der Waals. Our main result is the RPA potential energy surfaces of graphene on the Cu(111), Ni(111), Co(0001), Pd(111), Pt(111), Ag(111), Au(111), and Al(111) metal surfaces, which represent archetypical examples of metal-organic interfaces. Comparison with semilocal density approximations and a nonlocal van der Waals functional show that only the RPA captures both the weak covalent and dispersive forces, which are equally important for these systems. We benchmark our implementation in the gpaw electronic structure code by calculating cohesive energies of graphite and a range of covalently bonded solids and molecules as well as the dissociation curves of H2 and H2+. These results show that the RPA with orbitals from the local density approximation suffers from delocalization errors and systematically underestimates covalent bond energies yielding similar or lower accuracy than the Perdew-Burke-Ernzerhof (PBE) functional for molecules and solids, respectively.

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  • Received 27 November 2012

DOI:https://doi.org/10.1103/PhysRevB.87.075111

©2013 American Physical Society

Authors & Affiliations

Thomas Olsen* and Kristian S. Thygesen

  • Center for Atomic-Scale Materials Design (CAMD) and Center for Nanostructured Graphene (CNG), Department of Physics, Technical University of Denmark, DK–2800 Kongens Lyngby, Denmark

  • *tolsen@fysik.dtu.dk

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Vol. 87, Iss. 7 — 15 February 2013

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