π–π* Circular dichroism of mono-olefins

Abstract

Calculations for a model and a few simple compounds show that a dynamical coupling mechanism contributes to the olefinic π–π* circular dichroism band to an amount comparable with the term due to twisting the double bond; they also provide a basis for both the Anderson model and the Scott–Wrixon octant rule. Of three sets of bond polarisabilities tested, the set with carbon–carbon single bond and carbon–hydrogen bond anisotropies taken as negative and zero respectively, provides the best correlation with experimental values. The results and implications of these calculations are discussed.