DFT study of the adsorption and dissociation of 5-hydroxy-3-butanedithiol-1,4-naphthaquinone (Jug-C4-thiol) on Au(111) surface
Density functional theory has been used to investigate the adsorption and dissociation of 5-hydroxy-3-hexanediol-1,4-naphthaquinone (Jug-C4-thiol) at a coverage of p(4 × 4) on a Au(111) surface. Both physisorption and chemisorption processes are investigated. For each process, the surface energy potential is explored by an exhaustive test of the adsorption site. The most favorable site is found to be face-centered cubic. The adsorption energies are less than − 0.20 eV in the case of physisorption, while they range from − 1.70 to − 1.92 eV for chemisorption. The effect of the naphthoquinone function is negligible in the adsorption process. The alkyl chain inhibits electron delocalization between the surface and the conjugated head of the molecule. Analysis of the bonding shows the formation of two ionocovalent bonds between the sulfur and the gold atoms. The thermodynamics and kinetics of S–H bond dissociation are studied. The results reveal that adsorption involves a dissociation path in which a hydrogen atom moves to the most neighboring site and a hydrogen atom migrates to its most stable site. The maximum barrier energy of the first step is less than 2.7 eV while the migration barrier does not exceed 0.5 eV.
KeywordsAdsorption Functional molecule Au (111) DFT Density of states NEB method
DFT calculations were performed using HPC resources from GENCI- [CCRT/CINES/IDRIS] (Grant 2017-[A0020807006]).
- Askerka, M., Pichugina, D., Kuz’menko, N., Shestakov, A.: Theoretical prediction of S–H bond rupture in methanethiol upon interaction with gold. J. Phys. Rev. A. 116, 7686–7693 (2012)Google Scholar
- Ktari, N., Fourati, N., Zerrouki, C., Ruan, M., Seydou, M., Barbaut, F., Nal, F., Yaakoubi, N., Chehimi, M.M., Kalfat, R.: Design of a polypyrrole MIP-SAW sensor for selective detection of flumequine in aqueous media: correlation between experimental results and DFT calculations. RSC Adv. 5, 88666 (2015)CrossRefGoogle Scholar
- Laibinis, P.E., Whitesides, G.M., Allara, D.L., Tao, Y.T., Parikh, A.N., Nuzzo, R.G.: Comparison of the structures and wetting properties of self-assembled monolayers of n-alkanethiols on the coinage metal surfaces, copper, silver, and gold. J. Am. Chem. Soc. 113, 7152–7167 (1991)CrossRefGoogle Scholar
- Porter, M.D., Bright, T.B., Allara, D.L., Chidsey, C.E.D.: Spontaneously organized molecular assemblies; 4. Structural characterization of n-alkyl thiol monolayers on gold by optical ellipsometry, infrared spectroscopy, and electrochemistry. J. Am. Chem. Soc. 109, 3559–3568 (1987)CrossRefGoogle Scholar
- Raouafi, F., Seydou, M., Lassoued, K., Taleb, A., Diawara, B.: First-principles investigation of methanethiol adsorption and dissociation mechanisms on the high-Miller-index vicinal surface Cu(4 1 0). J. Phys. 28, 175001–175012 (2016)Google Scholar
- Syomin, D., Kim, J., Koel, B.E., Ellison, G.B.: Identification of adsorbed phenyl (C6H5) groups on metal surfaces: electron-induced dissociation of benzene on Au(111). J. Phys. Rev. 105, 8387–8394 (2001)Google Scholar
- Vericat, C., Vela, M.E., Benitez, G.A., Gago, J.A.M., Torrelles, X., Alvarezza, R.C.: Surface characterization of sulfur and alkanethiol self-assembled monolayers on Au (111). J. Phys. 18, R867–R900 (2006)Google Scholar