Combining density functional and incremental post-Hartree-Fock approaches for van der Waals dominated adsorbate-surface interactions: Ag2/graphene
Résumé
A combined density functional (DFT) and incremental post-Hartree-Fock (post-HF) approach, proven
earlier to calculate He-surface potential energy surfaces [de Lara-Castells et al., J. Chem. Phys. 141,
151102 (2014)], is applied to describe the van der Waals dominated Ag2/graphene interaction. It
extends the dispersionless density functional theory developed by Pernal et al. [Phys. Rev. Lett.
103, 263201 (2009)] by including periodic boundary conditions while the dispersion is parametrized
via the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)]. Starting with
the elementary cluster unit of the target surface (benzene), continuing through the realistic cluster
model (coronene), and ending with the periodic model of the extended system, modern ab initio
methodologies for intermolecular interactions as well as state-of-the-art van der Waals-corrected
density functional-based approaches are put together both to assess the accuracy of the composite
scheme and to better characterize the Ag2/graphene interaction. The present work illustrates how
the combination of DFT and post-HF perspectives may be efficient to design simple and reliable ab
initio-based schemes in extended systems for surface science applications.