Models for the adsorption and self-assembly of ethanol and 1-decanethiol on Au(111) surfaces. A comparative study by computer simulation

• Published in: International journal of quantum chemistry 2010-02, Vol.110 (2), p.293-306
• Main Authors: Fartaria, Rui P. S., Freitas, Filomena F. M., Silva Fernandes, Fernando M. S.
• Format: Article
• Language: English
• Subjects: absorption; alkylthiol; ethanol; gold electrode; self-assembly
• ISSN: 0020-7608; 1097-461X
• DOI: 10.1002/qua.22254

Results from computer simulations, based on different models to study theadsorption and self‐assembly of the ethanol and 1‐decanethiol on gold surfaces, Au(111), are presented. Canonical ensemble Monte Carlo simulations were performed at 298 K using two different force fields. One from DFT calculations, where the gold electrode has an explicit structure (corrugated electrode), and the other representing an electrode, in which the structure is taken into account on an average way (flat electrode). The behavior of the ethanol adsorption on gold surfaces, with and without the 1‐decanethiol presence, is analyzed. The introduction of molecular flexibility is also discussed. The relative surface density for the ethanol oxygen, adsorbed on gold, and the density profiles, in different conditions, show that the structure of the surface has a fundamental role on the way the adsorption takes place, not only on the preferential adsorption sites of the surface but also on the ethanol distribution over the electrodes. Potentials of mean force have also been calculated for the two surface models, giving the free energy barriers to the 1‐decanethiol crossing of the solvent adsorption layers. The average tilt angle, obtained with a single thiol molecule in the simulation box, presents the values: ∼26° for the rigid molecule model and 74° ± 18° for the flexible one. These differences are analyzed. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010