Torsional potential and strain energy distribution in an extended chain under stress

Abstract

Torsional potentialV(ϕ) for the single bond transformation in an extended hexadecane, subjected to elongation, has been determined by molecular mechanics calculations. The stored elastic energy significantly modifies the potentialV(ϕ), the conformational energies and the barriers of transition. Apart from the “soft” torsional coordinate, elastic energy is also dissipated considerably by bond stretching and angle bending. Maximal variations of the valence coordinates occur in the vicinity of the torsional defect and dampen along the chain. At higher elongation, the gauche minimum on the potentialV(ϕ) disappears and the calculations predict the abrupt gauche to trans transition. The energetics of torsion of a deformed chain are compared with the experimental data on the hydrodynamic extension of polymers in dilute solution by elongational flow. The calculations also provide details of a single bond transformation mechanism at conformational interconversions in a long chain, proposed by Helfand.