Primitive models of chemical association .2. Polymerization into flexible chain molecules of prescribed length

The structural properties of the totally flexible sticky two-point (S2P) model for polymerization into chain molecules of fixed length are studied. The model is represented by an n-component mixture of hard spheres of the same size with species 2,...,n-1 bearing two attractive sticky sites A and B, randomly distributed on the surface. The hard spheres of species 1 and n have only one site per particle, site B for species 1 and site A for species n. Due to the specific choice for the attractive interaction, which is present only between site B of the particles of species a and site A of the particles of species a + 1, this version of the S2P model represents an associating fluid that polymerizes into freely jointed tangent hard-sphere chain molecules. The correlation functions of this model are studied at all degrees of association using a recently obtained general solution of the polymer Percus-Yevick (PPY) approximation [Yu. Kalyuzhnyi and P. Cummings, J. Chem. Phys. 103, 3265 (1995)]. Comparison of the results of the present theory in the complete association limit with corresponding computer-simulation results and results of other theories is presented and discussed. The complete-association results constitute a quantitatively successful theory of the mean monomer-monomer distribution functions for less than or equal to 16 but for n = 50 these functions are no longer quantitatively accurate. (C) 1997 American Institute of Physics.