Molecules near surfaces are regularly trapped in small cavitations. Molecular confinement, especially water confinement, shows intriguing and unexpected behavior including surface entropy adjustment; nevertheless, observations of entropic variation during molecular confinement are scarce. An experimental assessment of the correlation between surface strain and entropy during molecular confinement in tiny crevices is difficult because strain variances fall in the nanometer scale. In this work, entropic variations during water confinement in 2D nano/micro cavitations were observed. Experimental results and random walk simulations of water molecules inside different size nanocavitations show that the mean escaping time of molecular water from nanocavities largely deviates from the mean collision time of water molecules near surfaces, crafted by 157 nm vacuum ultraviolet laser light on polyacrylamide matrixes. The mean escape time distribution of a few molecules indicates a non-thermal equilibrium state inside the cavity. The time differentiation inside and outside nanocavities reveals an additional state of ordered arrangements between nanocavities and molecular water ensembles of fixed molecular length near the surface. The configured number of microstates correctly counts for the experimental surface entropy deviation during molecular water confinement. The methodology has the potential to identify confined water molecules in nanocavities with life science importance.
Keywords: AFM; VUV irradiation; electric dipole interactions; entropy; nanocavities; nanoindentation; nanothermodynamics; non-thermal equilibrium; random walk; water.