Vapor-liquid phase coexistence and transport properties of two- dimensional oligomers

TK Patra and A Hens and JK Singh, JOURNAL OF CHEMICAL PHYSICS, 137, 084701 (2012).

DOI: 10.1063/1.4747195

Grand-canonical transition-matrix Monte Carlo and histogram reweighting techniques are used herein to study the vapor-liquid coexistence properties of two-dimensional (2D) flexible oligomers with varying chain lengths (m = 1-8). The phase diagrams of the various 2D oligomers follow the correspondence state (CS) principle, akin to the behavior observed for bulk oligomers. The 2D critical density is not influenced by the oligomer chain length, which contrasts with the observation for the bulk oligomers. Line tension, calculated using Binder's formalism, in the reduced plot is found to be independent of chain length in contrast to the 3D behavior. The dynamical properties of 2D fluids are evaluated using molecular dynamics simulations, and the velocity and pressure autocorrelation functions are investigated using Green-Kubo (GK) relations to yield the diffusion and viscosity. The viscosity determined from 2D non-equilibrium molecular dynamics simulation is compared with the viscosity estimated from the GK relations. The GK relations prove to be reliable and efficient for the calculation of 2D transport properties. Normal diffusive regions are identified in dense oligomeric fluid systems. The influence of molecular size on the diffusivity and viscosity is found to be diminished at specific CS points for the 2D oligomers considered herein. In contrast, the viscosity and diffusion of the 3D bulk fluid, at a reduced temperature and density, are strongly dependent on the molecular size at the same CS points. Furthermore, the viscosity increases and the diffusion decreases multifold in the 2D system relative to those in the 3D system, at the CS points. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4747195

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