Adsorption of small aromatic molecules on gold: a DFT localized basis set study including van der Waals effects

Abstract

We compare the density functional theory (DFT) results on the adsorption of small aromatic molecules (benzene, pyridine and thiophene) on gold surfaces obtained by using three types of van der Waals exchange-correlation functionals and localized basis set calculations. We show that the value of the molecule-surface binding energy depends on the interplay between the BSSE effect and the tendency of the exchange-correlation functionals to overestimate both the molecule-surface as well as the gold-gold distances within the relaxed systems. Consequently, we find that by using different types of LCAO basis sets or geometric models for the adsorption of the molecules on the surface, the binding energy can vary up to 100 %. A critical analysis of the physical parameters resulting from the calculations is presented for each exchange-correlation functional.

Translation of metal-phthalocyanines adsorbed on Au(111): from van der Waals interaction to strong electronic correlation

“…We used the van der Waals exchange-correlation functional of Berland and Hyldgaard (BH) 41 . During our tests we found that the BH functional correctly describes the geometric structure of the metallic bulks and surfaces which is a major advantage in the study of molecular adsorption 42 .…”

“…The binding energy for the adsorbed molecules, Δ , was computed by taking into account the BSSE effect as well as the molecular deformation upon adsorption 42 , 46 (see Supplementary material for technical details).…”

Bonding of Gold Nanoclusters on Graphene with and without Point Defects

“…The inclusion of van der Waals interactions is an important part of this work. They are known to play a role in the adsorption of small aromatic molecules on Au surfaces [ 27 ], the catalytic selectivity for the oxidation of organic molecules on metallic Au [ 28 ], the electronic and energetic properties of small Au NPs [ 29 ], and to be competing with covalent and ionic bonds for bonding on Au–S surfaces and Au NPs [ 30 ].…”

Comparative Analysis of Reactant and Product Adsorption Energies in the Selective Oxidative Coupling of Alcohols to Esters on Au(111)

“…Weak van der Waals interactions, typically ignored in the presence of covalent bonds, take center stage in determining the favorable adsorption sites on the catalyst surfaces. In addition to catalyst design, noncovalent interactions between organic molecules and planar single crystal metal surfaces have also been recently studied in the context of self-assembled monolayer (SAM) systems and identified as the principal factor in determining the assembly patterns [30][31][32][33][34].…”