The equation of state of flexible chains of tangent hard spheres at high-density region from simulation and thermodynamic perturbation theory

Abstract

Radial and triplet correlation functions of the reference hard sphere system are determined at several solid densities by canonical Monte Carlo (MC) simulations. These customized data are used to extend the second order thermodynamic perturbation theory (TPT) to the solid phase of flexible hard chain systems. In order to test the accuracy of the TPT equation of state (EOS) for hard chains, MC simulations are carried out for systems of chain length 4 to 15. Several simulations are performed in the isobaric-isothermal ensemble to obtain the high-density EOS of hard chains in the fluid and solid phases. To determine solid-fluid equilibrium (SFE), Helmholtz free energies of solid crystals at a reference density are determined in a series of canonical MC simulations. As the chain length increases, asymptotic behaviors are observed in the coexistence pressure and densities of fluid and solid phases. It is found that the accuracy of TPT for EOS and SFE in systems of hard chains greatly improves by extending it to second order.