title: The isotropic-nematic phase transition of tangent hard-sphere chain fluids--pure components.
abstract: An extension of Onsager's second virial theory is developed to describe the isotropic-nematic phase transition of tangent hard-sphere chain fluids. Flexibility is introduced by the rod-coil model. The effect of chain-flexibility on the second virial coefficient is described using an accurate, analytical approximation for the orientation-dependent pair-excluded volume. The use of this approximation allows for an analytical treatment of intramolecular flexibility by using a single pure-component parameter. Two approaches to approximate the effect of the higher virial coefficients are considered, i.e., the Vega-Lago rescaling and Scaled Particle Theory (SPT). The Onsager trial function is employed to describe the orientational distribution function. Theoretical predictions for the equation of state and orientational order parameter are tested against the results from Monte Carlo (MC) simulations. For linear chains of length 9 and longer, theoretical results are in excellent agreement with MC data. For smaller chain lengths, small errors introduced by the approximation of the higher virial coefficients become apparent, leading to a small under- and overestimation of the pressure and density difference at the phase transition, respectively. For rod-coil fluids of reasonable rigidity, a quantitative comparison between theory and MC simulations is obtained. For more flexible chains, however, both the Vega-Lago rescaling and SPT lead to a small underestimation of the location of the phase transition.
authors.affiliation: Process and Energy Laboratory, Delft University of Technology, Leeghwaterstraat 44, 2628 CA Delft, The Netherlands.
authors.forename: Thijs
authors.initials: T
authors.lastname: van Westen
authors.forename: Bernardo
authors.initials: B
authors.lastname: Oyarzún
authors.forename: Thijs J H
authors.initials: TJ
authors.lastname: Vlugt
authors.forename: Joachim
authors.initials: J
authors.lastname: Gross