Molecular dynamics investigation of benzoic acid in confined spaces

Classical molecular dynamics simulations are carried out to investigate the aggregation of supercooled benzoic acid in confined spaces. Nanocavities, nanotubes and nanolayers are defined by restricting the periodicity of the simulation to zero, one or two dimensions, with boundaries set by adjustable, general, and computationally cheap van der Waals barriers. The effect of different confinement geometries is explored. It is found that the confinement impacts the liquid collective dynamics, strengthening the correlations that affect the motion of distant molecules. Overall, confinement determines up to a tenfold increase of the viscosity of the liquid and strongly slows down the rotational correlation times. Aggregation mediated by interactions with the walls and partial polarization of the liquid are observed. Additionally, transitions to high-density liquid states occur when stiffer barriers are used. In general, a reduced accessible amount of phase space fosters the struggle for a closer packing to relieve unfavorable atom-atom contacts, while maximizing the attractive ones. In benzoic acid, this implies that the hydrogen bond network is organized more efficiently in high density states. The confinement of supercooled benzoic acid increases the dynamic viscosity and the rotational correlation. Liquid-liquid transitions are observed within the nanocavity, mediated by the molecule-barrier interactions.