A non-additive repulsive contribution in an equation of state: The development for homonuclear square well chains equation of state validated against Monte Carlo simulation

Thi-Kim-Hoang Trinh (1, 2) , Jean-Philippe Passarello (1) , Jean-Charles de Hemptinne (2) , Rafael Lugo (2) , Véronique Lachet (2)

1 LSPM - Laboratoire des Sciences des Procédés et des Matériaux
2 IFPEN - IFP Energies nouvelles

This work consists of the adaptation of a non-additive hard sphere theory inspired by Malakhov and Volkov, Polym. Sci. Ser. A. 2007;49(6):745-756 to a square-well chain. Using the thermodynamic perturbation theory, an additional term is proposed that describes the effect of perturbing the chain of square well spheres by a non-additive parameter. In order to validate this development, NPT Monte Carlo simulations of thermodynamic and structural properties of the non-additive square well (NASW) for a pure chain and a binary mixture of chains are performed. Good agreements are observed between the compressibility factor originating from the theory and those from molecular simulations.

Mots clés: Monte Carlo simulation; compressibility factor; inter-segment distribution function; Square–well potential; non-additive parameter

Domaines: Chimie théorique et/ou physique

Thi-Kim-Hoang Trinh, Jean-Philippe Passarello, Jean-Charles de Hemptinne, Rafael Lugo, Véronique Lachet. A non-additive repulsive contribution in an equation of state: The development for homonuclear square well chains equation of state validated against Monte Carlo simulation. Journal of Chemical Physics, 2016, 144, pp.124902. ⟨10.1063/1.4944068⟩. ⟨hal-01339980⟩