Hydrodynamic properties of supercoiled linear polymer molecules

The Rouse-Bueche-Zimm spring-bead model has been extended to include both excluded volume and the chain stiffness. A dynamic model including the first- and the second-nearest neighbor spring-bead interactions together with the excluded volume forces between the nonadjacent beads is developed. The calculation is made using the normal coordinate method of Zimm, and applied to linear macromolecules. The sum and the square of the sum of the inverse eigenvalues are tabulated for various N (N being the number of chain elements) as a function of excluded volume and chain stiffness. These sums decrease as either the chain stiffness or the excluded volume increases. The Flory parameter (φC× 10−23) is computed as a function of increasing chain stiffness and excluded volume, and it is concluded that this parameter decreases as both chain stiffness and excluded volume increase. However, the effect of excluded volume is more pronounced than the chain stiffness.