Dresden 2017 – wissenschaftliches Programm
HL 73: Electronic-Structure Theory: New Concepts and Developments in Density Functional Theory and Beyond - VI
HL 73.2: Vortrag
Donnerstag, 23. März 2017, 10:45–11:00, GER 38
Using Dipsersion-Corrected Density Functional Theory to Understand the Phase Diagram of Alkanethiolates on Gold — •Joakim Löfgren, Henrik Grönbeck, Kasper Moth-Poulsen, and Paul Erhart — Chalmers University of Technology, Gothenburg, Sweden
A key challenge in modern computational materials chemistry is the description of van der Waals interactions in density functional theory simulations, where the failure of conventional exchange-correlation functionals is well-known. While, in the recent years, several methods have been proposed for overcoming these difficulties, the applications are becoming increasingly more demanding as well. An important example is that of ligand-protected nanoparticles, which typically feature metallic, covalent as well as dispersive interactions that should all, ideally, be treated on an equal footing. In this work we show that significant progress can be made in this direction: with the aid of the recently-developed vdW-DF-cx functional we study the phase diagram of self-assembled monolayers of alkanethiolates on gold. This system is important for practical applications and as a general representative of self-assembly at a metal surface. In particular, a quantitative description of the dispersion-driven phase transition between a lying-down and a standing-up monolayer is obtained using an ab inito thermodynamics framework. The results are shown to be in good agreement with experimental data and highlight that accurately accounting for dispersive interactions is both feasible and a crucial part of modeling self-assembled systems.