Energetically and pressure driven phase transitions in molecularly thin films of n-alkanes

Abstract

Molecular dynamics simulations were carried out on molecularly thin films of n-octane confined between topographically smooth solid surfaces. We focused on determining the effect of increasing solid surface-methylene unit energetic affinity and the effect of increasing pressure (normal load) of the film in inducing liquid-solid phase transitions. Simulations of films wide enough to accomodate three segmental layers showed an abrupt transition in the structural features at a critical value of the characteristic energy that quantified the affinity between solid surfaces and methylene units. This energetically driven transition was evident from the discontinuous increase of intermolecular order, a precipitous extension of the octane molecules and freezing of molecular migration and rotation. Increasing pressure had a similar effect in inducing a liquid-solid phase transition. The characteristics of the transition showed that it is a mild first-order transition from a highly ordered liquid to a poorly organized solid. These findings demonstrate that the solidification of nanoscopically thin films of linear alkanes is a general phenomenon (driven either energetically or by increasing pressure), and does not require the aid of commensurate surface topography. Our findings on relatively wider films (5 segmental diameters wide) show that the interfacial layer undergoes a similar first-order phase transition with increasing solid-methylene unit energetic affinity. This energy threshold is significantly higher than the one observed in thin film simulations.