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It is well-known that the interaction between passivated nanoparticles can betuned by their complete immersion in a chosen solvent, such as water. Whatremains unclear on a molecular level is how nanoparticle interactions may bealtered in the presence of solvent vapor where complete immersion is notachieved. In this paper, we report an all-atom molecular dynamics simulationstudy of the change in pair potential of mean force between dodecane thiolligated gold nanoparticles (AuNPs) when exposed to water vapor. With theequilibrium vapor pressure of water at 25 \degree C, there is very rapidcondensation of water molecules onto the surface of the AuNPs in the form ofmobile clusters of 100-2000 molecules that eventually coalesce into a few largeclusters. When the distance between two AuNPs decreases, a water clusterbridging them provides an adhesive force that increases the depth and altersthe shape of the pair-potential of mean force. That change of shape includes adecreased curvature near the minimum, consistent with experimental data showingthat cyclic exposure to water vapor and its removal reversibly decreases andincreases the Young's modulus of a freely suspended self-assembled monolayer ofthese AuNPs.

Influence of Water Vapor on the Interaction Between Dodecane Thiol Ligated Au Nanoparticles