Density Functional Theory with Modified Dispersion Correction for Metals Applied to Self-Assembled Monolayers of Thiols on Au(111). (23rd September 2013)

• Record Type: Journal Article
• Authors: Andersson, M. P.
• Other Names: Ge Qingfeng Academic Editor.; Kokalj Anton Academic Editor.; Koyama Michihisa Academic Editor.
• Is Part Of: Journal of theoretical chemistry. Volume 2013(2013)
• Publication Date: 2013-09-23
• Subjects: Chemistry, Physical and theoretical -- Periodicals; Chemistry, Physical and theoretical; Periodicals; Electronic journals; 541.2
• DOI: 10.1155/2013/327839
• Languages: English
• ISSNs: 2356-7686

Abstract

Abstract : Using sound physical principles we modify the DFT-D2 atom pairwise semiempirical dispersion correction to density functional theory to work for metallic systems and in particular self-assembled monolayers of thiols on gold surfaces. We test our approximation for two functionals PBE-D and revPBE-D for lattice parameters and cohesive energies for Ni, Pd, Pt, Cu, Ag, and Au, adsorption energies of CO on (111) surfaces of Pd, Pt, Cu, Ag, and Au, and adsorption energy of benzene on Ag(111) and Au(111). Agreement with experimental data is substantially improved. We apply the method to self-assembled monolayers of alkanethiols on Au(111) and find reasonable agreement for PBE-D and revPBE-D for both physisorption of n-alkanethiols as well as dissociative chemisorption of dimethyl disulfide as an Au-adatom-dithiolate complex. By modifying theC 6 coefficient for Au, we obtain quantitative agreement for physisorption and chemisorption for both PBE-D and revPBE-D using the same set of parameters. Our results confirm that inclusion of dispersion forces is crucial for any quantitative analysis of the thiol and thiolate bonds to the gold surface using quantum chemical calculations.