Equilibrium and Dynamical Characteristics of Imidazole Langmuir Monolayers on Graphite Sheets

Using molecular dynamics techniques, we examine structural and dynamical characteristics of liquid-like imidazole (Im) monolayers physisorbed onto a planar graphite sheet, at T = 384 K. Our simulations reveal that molecular orientations in the saturated monolayer exhibit a bistable distribution, characterized by an inner parallel arrangement of the molecules in close contact with the substrate and a slanted alignment, in those lying in adjacent, outer locations. Compared to the results found in three-dimensional, bulk phases, the analysis of the spatial correlations between sites participating in hydrogen bonding shows a clear enhancement of the intermolecular interactions, which also leads to stronger dipolar correlations. As a result, the gross structural features of the monolayer can be cast in terms of mesoscopic domains, comprising units articulated via winding hydrogen bonds, that persist along typical time intervals of a few tens of picoseconds. On the dynamical side, a similar comparison of the characteristic decorrelation time for orientational motions shows a 4-fold increment. Contrasting, the reduction of the system dimensionality leads to a larger diffusion constant. Possible substrate-induced anisotropies in the diffusive motions are also investigated.