Wavelength resolved specific optical rotations and homochiral equilibria

Abstract

The fundamental expressions governing specific optical rotations (SORs) of homochiral systems exhibiting monomer–dimer equilibria are presented. These equations are then utilized with the experimental measurements of wavelength resolved circular birefringence for (R)-(−)-α-hydroxy-β,β-dimethyl-γ-butyrolactone, to determine the wavelength resolved SORs of monomer and dimer components for the first time. Density functional theory predictions on the corresponding dispersion properties of monomer and dimer are found to match with experimentally determined quantities within a factor of ∼2. The wavelength resolved circular birefringence in the liquid solution phase thus provides a powerful means to investigate the molecular properties involved in homochiral equilibria.