Microscopic origin of the effect of substrate metallicity on interfacial free energies - Sorbonne Université
Journal Articles Proceedings of the National Academy of Sciences of the United States of America Year : 2021

Microscopic origin of the effect of substrate metallicity on interfacial free energies

Abstract

We investigate the effect of the metallic character of solid substrates on solid–liquid interfacial thermodynamics using molecular simulations. Building on the recent development of a semiclassical Thomas–Fermi model to tune the metallicity in classical molecular dynamics simulations, we introduce a thermodynamic integration framework to compute the evolution of the interfacial free energy as a function of the Thomas–Fermi screening length. We validate this approach against analytical results for empty capacitors and by comparing the predictions in the presence of an electrolyte with values determined from the contact angle of droplets on the surface. The general expression derived in this work highlights the role of the charge distribution within the metal. We further propose a simple model to interpret the evolution of the interfacial free energy with voltage and Thomas–Fermi length, which allows us to identify the charge correlations within the metal as the microscopic origin of the evolution of the interfacial free energy with the metallic character of the substrate. This methodology opens the door to the molecular-scale study of the effect of the metallic character of the substrate on confinement-induced transitions in ionic systems, as reported in recent atomic force microscopy and surface force apparatus experiments.
Fichier principal
Vignette du fichier
Scalfi et Rotenberg - 2021 - Microscopic origin of the effect of substrate meta.pdf (3.39 Mo) Télécharger le fichier
Origin Files produced by the author(s)

Dates and versions

hal-03477956 , version 1 (13-12-2021)

Identifiers

Cite

Laura Scalfi, Benjamin Rotenberg. Microscopic origin of the effect of substrate metallicity on interfacial free energies. Proceedings of the National Academy of Sciences of the United States of America, 2021, 118 (50), pp.e2108769118. ⟨10.1073/pnas.2108769118⟩. ⟨hal-03477956⟩
105 View
641 Download

Altmetric

Share

More