| Zugriffsnummer | 52293 |
| Dokumenttyp | Zeitschriftenartikel |
| Peer Review | mit Peer Review |
| Sprache | Englisch |
| Titel | The thermodynamics of self-assembled monolayer formation: a computational and experimental study of thiols on a flat gold surface |
| Autor(in); Institution |
Zoccante, Alberto; Università del Piemonte Orientale, Vercelli, ITALY
Cara, Eleonora; Istituto Nazionale di Ricerca Metrologica (INRiM), Torino, ITALY
Ferrarese Lupi, Federico; Istituto Nazionale di Ricerca Metrologica (INRiM), Torino, ITALY
Beckhoff, Burkhard; 7.2, Röntgenmesstechnik mit Synchrotronstrahlung, PTB-Berlin
Giovannozzi, Andrea; Quantum Metrology and Nanotechnologies, Istituto Nazionale di Ricerca Metrologica (INRiM), Turin, ITALY
Klapetek, Petr; Czech Metrology Institute, Brno, CZECH REPUBLIC
Marchi, Davide; Università del Piemonte Orientale, Vercelli, ITALY
Cossi, Maurizio; Università degli Studi del Piemonte Orientale, Vercelli, ITALY
|
| Quelle/Jahr | Physical Chemistry, Chemical Physics: 26 (2024), 27, 18799 - 18807 |
| ISSN | 1463-9076 |
| DOI | |
| Verlag | London: Royal Society of Chemistry |
| Zusammenfassung | A methodology based on molecular dynamics simulations is presented to determine the chemical potential of thiol self-assembled monolayers on a gold surface. The thiol de-solvation and then the monolayer formation are described by thermodynamic integration with a gradual decoupling of one molecule from the environment, with the necessary corrections to account for standard state changes. The procedure is applied both to physisorbed undissociated thiol molecules and to chemisorbed dissociated thiyl radicals, considering in the latter case the possible chemical potential of the produced hydrogen. We considered monolayers formed by either 7-mercapto-4-methylcoumarin (MMC) or 3-mercapto-propanoic acid (MPA) on a flat gold surface: the free energy profiles with respect to the monolayer density are consistent with a transition from a very stable lying-down phase at low densities to a standing-up phase at higher densities, as expected. The maximum densities of thermodynamically stable monolayers are compared to experimental measures performed with reference-free grazing-incidence X-ray fluorescence (RF-GIXRF) on the same systems, finding a better agreement in the case of chemisorbed thiyl radicals. |
| Kostenfreier Zugang | Open Access Hybrid |
| Rechteinformation | CC BY 4.0 ; Creative Commons Attribution 4.0 License |
| Themenbereich der Metrologie | Photometrie und Radiometrie |
Zitierung
Zoccante, A., Cara, E., Ferrarese Lupi, F., Hönicke, P., Kayser, Y., Beckhoff, B., Giovannozzi, A., Klapetek, P., Marchi, D., & Cossi, M. (2024). The thermodynamics of self-assembled monolayer formation: a computational and experimental study of thiols on a flat gold surface. Physical Chemistry, Chemical Physics, 26(27), 18799–18807. https://doi.org/10.1039/D4CP01322K