The Circular Dichroism of the Carbonyl n-π* Transition

Abstract

An independent systems/perturbation approach is used to determine analytic expressions for the circular dichroism (CD) of the n-π* transition in carbonyl compounds. It is shown that all available experimental data can be understood in terms of the predictions made by this theory. In general, for uncharged, nonpolar systems, the CD varies according to the octant sector rule of Moffitt et al.;1however, exceptions to this rule do arise for certain geometries and for situations in which the substituents on the compounds exclude the solvent in an unsymmetrical manner. Different geometry dependences are derived for polar and charged species and are found to explain the existing data. Show more