Poly , exclusion distance

For poly(methylene), an exclusion distance (hard sphere diameter) of 2.00 A was used to prevent overlap of methylene residues. The calculation reproduced the accepted theoretical and experimental characteristic ratios (mean square unperturbed end-to-end distance relative to that for a freely jointed gaussian chain with the same number of segments) of 5.9. This wps for zero angular bias and a trans/gauche energy separation of 2.09 kJ mol". ... 

A preferable system is poly(p-fluorostyrene) doped into poly(styrene). Since rotations about the 1,4 phenyl axis do not alter the position of the fluorine, the F spin may be regarded as being at the end of a long "bond" to the backbone carbon. In standard RIS theory, this polymer would be treated with dyad statistical weights to automatically take into account conformations of the vinyl monomer unit which are excluded on steric grounds. We have found it more convenient to retain the monad statistical weight structure employed for the poly(methylene) calculations. The calculations reproduce the experimental unperturbed dimensions quite well when a reasonable set of hard sphere exclusion distances is employed. 

FIG. 1 Variation of the local concentration, C, of the monovalent counterion of radius 0.3 nm with the radial distance, r, from the axis of the cylindrical polyion of radius a = 0.8 nm. The average counterion concentration is marked by Cav, d is the exclusion distance from the polyion axis to the center of the counterion, and/is the fraction of free counterions. The value of the charge density parameter A = 2.83 is typical for aqueous solutions of poly(styrenesulfonates) at 25°C, and the value of the radius of the cell R = 65.2 nm corresponds to the polyelectrolyte concentration CP = 5 X 10 4 monomol dm3. 

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