The Thermodynamics of Self Assembled Monolayers Formation: A computational and Experimental Study of Thiols on Flat Gold Surface

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00177016%3A_____%2F24%3AN0000140" target="_blank" >RIV/00177016:_____/24:N0000140 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlehtml/2024/cp/d4cp01322k" target="_blank" >https://pubs.rsc.org/en/content/articlehtml/2024/cp/d4cp01322k</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/D4CP01322K" target="_blank" >10.1039/D4CP01322K</a>

Jazyk výsledku

angličtina

Název v původním jazyce

The Thermodynamics of Self Assembled Monolayers Formation: A computational and Experimental Study of Thiols on Flat Gold Surface

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

The Thermodynamics of Self Assembled Monolayers Formation: A computational and Experimental Study of Thiols on Flat Gold Surface

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)

Projekt

<a href="/cs/project/9B22001" target="_blank" >9B22001: Operando metrology for energy storage materials</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Physical Chemistry Chemical Physics

ISSN

—

e-ISSN

1463-9084

Svazek periodika

2024

Číslo periodika v rámci svazku

26

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

9

Strana od-do

18799-18807

Kód UT WoS článku

001257272100001

EID výsledku v databázi Scopus

2-s2.0-85197081773