Hypochromism and optical rotation in helical polymers

Abstract

We show that the decreased light absorption and the anomalous optical rotatory dispersion in helical polynucleotides and polypeptides may be interpreted purely as a local field effect. The electric field of the incident light wave is screened off from each residue by the induced electric dipoles in the others. Quantum-mechanical calculations based on time-dependent Hartree theory and this local field picture correspond precisely with the formulae derived in Tinoco's, Rhodes's, and Moffitt's exciton theories, provided that the Coulomb interactions are small. The degenerate exciton waves in our theory correspond to normal modes of a set of coupled oscillators, and the rotational strengths and oscillator strengths are conserved. There is no conflict between Tinoco's theory of hypochromism and the ones proposed by Bolton and Weiss and by Nesbet. One new conclusion is that the energy shifts accompanying hypochromism should not vary much when the exciton coupling changes from the strong to the weak coupling limits.