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Journal of Chemical Physics, Vol.118, No.23, 10794-10807, 2003
Integral equation theories for monodisperse and polydisperse sticky hard sphere chain fluid: Thermodynamic and structural properties in the polymer Percus-Yevick and ideal chain approximations
The thermodynamic and structural properties of a freely jointed homonuclear sticky hard sphere chain fluid are studied using one-component and multi-component multi-density Ornstein-Zernike integral equation theories. In this formalism, a polydisperse chain fluid is modeled as a one-component system of associating sticky hard spheres with finite association strength, while a monodisperse system is modeled as an equal molar m-component mixture of associating sticky hard spheres with infinite association strength in the complete association limit. General analytical solutions to both models are obtained within the polymer Percus-Yevick and ideal chain approximations. Explicit analytical expressions for the contact values of correlation functions are obtained. The coordination number around a sticky hard sphere is calculated and its relationship with the contact value of the correlation function is discussed. Both intermolecular and intramolecular correlation functions beyond the hard core region are calculated numerically. Radial distribution functions of monodisperse dimer and tetramer are compared with those of polydisperse chains (with mean chain lengths of 2 and 4), and it is found that significant discrepancy exists at low density. This disparity, however, diminishes as chain density increases. The Helmholtz energy and pressure of monodisperse homonuclear chains are obtained via the energy route. The critical temperature, critical density, and phase coexistence of the fluid are also obtained. (C) 2003 American Institute of Physics.