Equationof state and Helmholtz energy functional for fused heterosegmented hard chains.

Abstract

Modern equationsof state for real nonspherical molecules are often based on Wertheim's first-order thermodynamic perturbation theory (TPT1). A major drawback of TPT1 is that it assumes tangentially bonded spheres. In this work, we develop a Helmholtz energy functional for systems comprising hard heterosegmented chains with arbitrary bond lengths. This is achieved by using hard-sphere fragments (i.e., hard spheres with spherical caps removed at the intersection to their neighbors) as monomers as opposed to full hard spheres. The model is written as a Helmholtz energy functional for inhomogeneous systems and the equationof state for a homogeneous system is determined as a special case. We thereby obtain an equationof state that can be used as a reference to develop statistical associating fluid theory models that more accurately describe the thermodynamic properties of nonspherical molecules. The model is validated against molecular simulation results of bulk pressures and density profiles in slit pores. For the bulk pressures, we show that the equationof state is in excellent agreement with results from molecular simulation for dimers, trimers, and chains of up to 20 segments. The density profiles of individual segments of the chains are regarded in slit pores. Some deviations of the theory from results of molecular simulations are observed for strongly fused chains. Overall, however, good agreement is found for inhomogeneous systems.