Nanocavity networks in 2D surfaces are responsible for molecular confinement, where molecules are normally trapped in small size caverns. Molecular confinement is responsible for a non-thermodynamic equilibrium local fluctuating–domain of trapped molecules characterised by chaotic behaviour at the boundary of 2D interphase. In this work, random walk simulations of mean escape time of only-once trapped water molecules in different size nanocavities is largely deviating from the mean escape time or repetitively trapped molecules and the mean collision time of molecules outside the cavities, where a thermodynamic equilibrium state is applied. The time differentiation inside and outside nanocavities adds a state of ordered arrangements, thus introducing an interplay between the thermodynamic (external domain) and the chaotic state (2D surface-domain). The divergence of molecular microstates from different trapping states agrees with an experimental surface entropy deviation during molecular confinement. Overall, a 2D photonic-crafted surface defines a topological surface with large fractal dimension (~2.8), where the characteristic time of processes abruptly jumps from a thermodynamic state to a chaotic one.
