Resolving the structure-energy dilemma at organic-inorganic interfaces: Adsorption of benzene, thiophene, and xenon over coinage metal surfaces
arXiv:2101.00600 · doi:10.1063/5.0042719
Abstract
Semilocal (SL) density functional approximations (DFAs) are widely applied but have limitations due to their inability to incorporate long-range van der Waals (vdW) interaction. Non-local functionals (vdW-DF, VV10, rVV10) or empirical methods (DFT+D, DFT+vdW, DFT+MBD) are used with SL-DFAs to account for such missing interaction. The physisorption of a molecule on the surface of the coinage metals (Cu, Ag, and Au) is a typical example of systems where vdW interaction is significant. However, it is difficult to find a general method that reasonably describes both adsorption energy and geometry of even the simple prototypes of cyclic and heterocyclic aromatic molecules like benzene (C6H6) and thiophene (C4H4S) respectively, with reasonable accuracy. In this work, we present an alternative scheme based on Zaremba-Kohn's theory, called DFT+vdW-dZK. We show that, unlike other popular methods, DFT+vdW-dZK and particularly SCAN+vdW-dZK gives an accurate description of the physisorption of a rare-gas atom (Xe) and two small albeit diverse prototype organic molecules on the (111) surfaces of the coinage metals.
References in corpus (8)
- Restoring the density-gradient expansion for exchange in solids and surfaces
- Generalized gradient approximation for solids and their surfaces
- A Higher-Accuracy van der Waals Density Functional
- Nonlocal van der Waals density functional: The simpler the better
- Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory
- Rehabilitation of PBE-GGA for Layered Materials
- Insight into the description of van der Waals forces for benzene adsorption on transition metal (111) surfaces
- First-principles study of mechanical and electronic properties of bent monolayer transition metal dichalcogenides