Molecular dynamics simulations of ultrathin free-standing layers made of melted (373.15-673.15 K) polyethylene chains, which exhibit a lower melting temperature (compared to the bulk value), were carried out to investigate the dominant pressure forces that shape the conformation of chains at the interfacial and bulk liquid regions. We investigated layer thicknesses, tL, from the critical limit of mechanical stability up to lengths of tens of nm and found a normal distribution of bonds dominated by slightly stretched chains across the entire layer, even at large temperatures. In the bulk region, the contribution of bond vibrations to pressure was one order of magnitude larger than the contributions from interchain interactions, which changed from cohesive to noncohesive at larger temperatures just at a transition temperature that was found to be close to the experimentally derived onset temperature for thermal stability. The interchain interactions produced noncohesive interfacial regions at all temperatures in both directions (normal and lateral to the surface layer). Predictions for the value of the surface tension, γ, were consistent with experimental results and were independent of tL. However, the real interfacial thickness-measured from the outermost part of the interface up to the point where γ reached its maximum value-was found to be dependent on tL, located at a distance of 62 Å from the Gibbs dividing surface in the largest layer studied (1568 chains or 313,600 bins); this was ~4 times the length of the interfacial thickness measured in the density profiles.
Keywords: free-standing layers; molecular dynamics; polyethylene; pressure; surface tension; thermal stability; vapor/liquid equilibria.