Interaction between dilute water vapor and dodecane thiol ligated Au nanoparticles: Hydrated structure and pair potential of mean force.

The interaction between two ligated nanoparticles depends on whether they are isolated or immersed in a liquid solvent. However, very little is known about the influence of solvent vapor on the interaction between two ligated nanoparticles. Recent experiments yield the surprising result that the cyclic exposure of solvent free suspended monolayers of dodecane thiol ligated gold nanoparticles (AuNPs) to water vapor and dry nitrogen generates reversible cyclic decreases and increases in Young’s modulus of the monolayer, implying corresponding cyclic changes in the AuNP–AuNP interaction. We examine how water vapor interacts with an isolated dodecane thiol dressed AuNP and how water vapor affects the interaction between a pair of nanoparticles, using all-atom molecular-dynamics simulations. We find that there is condensation of water molecules onto the ligand shell of an AuNP in the form of clusters of 100–2000 molecules that partially cover the shell, with most of the water in a few large clusters. A water cluster bridges the AuNPs, with a sensibly constant number of water molecules for AuNP–AuNP separations from the edge-to-edge contact up to center-to-center separations of 100 A. The wet AuNP–AuNP interaction has a slightly deeper and wider asymmetric well than does the dry interaction, a change that is qualitatively consistent with that implied by the observed water vapor induced change in Young’s modulus of a monolayer of these AuNPs. We find that macroscopic analyses of water drop–deformable surface interactions and dynamics provide both guidance to understanding and qualitatively correct predictions of the phenomena observed in our simulations.