Jingyu Wan | Searcharxiv

arXiv2026

Resolving Discrepancies in Disjoining Pressure Predictions for Liquid Nanofilms from Molecular Simulations

Literature values of disjoining pressure in liquid nanofilms from different molecular simulation methods show significant discrepancies. We demonstrate that these arise from neglecting long-range dispersion interactions and inconsistent definitions of film thickness in the original Peng method. A key insight is that long-range dispersion affects surface tension in a thickness-dependent manner, increasing it at large thickness but suppressing its enhancement at small thickness due to disjoining-pressure-induced normal compression and lateral expansion. This leads to crossover behavior in the surface tension of water nanofilms. Since disjoining pressure is obtained from the derivative of surface tension with respect to thickness, this nontrivial dependence strongly impacts its accuracy. With proper treatment of dispersion interactions and a consistent thickness definition, the revised Peng method agrees with the Bhatt method and yields more accurate Hamaker constants.

physics.chem-ph↗

arXiv2023

Molecular modeling of interfacial properties of the hydrogen+water+decane mixture in three-phase equilibrium

The understanding of geochemical interactions between H2 and geofluids is of great importance for underground H2 storage but requires further study. We report the first investigation on the three-phase fluid mixture containing H2, H2O, and n-C10H22. Molecular dynamics simulation and PC-SAFT density gradient theory are employed to estimate the interfacial properties under various conditions (temperature ranges from 298 to 373 K and pressure is up to around 100 MPa). Our results demonstrate that interfacial tensions (IFTs) of the H2-H2O interface in the H2+H2O+C10H22 three-phase mixture are smaller than IFTs in the H2+H2O two-phase mixture. This decrement of IFT can be attributed to C10H22 adsorption in the interface. Importantly, H2 accumulates in the H2O-C10H22 interface in the three-phase systems, which leads to weaker increments of IFT with increasing pressure compared to IFTs in the water+C10H22 two-phase mixture. In addition, the IFTs of the H2-C10H22 interface are hardly influenced by H2O due to the limited amount of H2O dissolved in bulk phases. Nevertheless, relatively strong enrichments and positive surface excesses of H2O are seen in the H2-C10H22 interfacial region. Furthermore, the values of the spreading coefficient are mostly negative revealing the presence of the three-phase contact for the H2+H2O+C10H22 mixture under studied conditions.

physics.chem-ph↗