Polarizable Continuum Model (PCM) Calculations of Solvent Effects on Optical Rotations of Chiral Molecules

A new theory of solvent effects on the optical rotations of chiral molecules is presented. The frequency-dependent electric dipole−magnetic dipole polarizability, βαβ(ν), is calculated using density functional theory (DFT). Solvent effects are included using the polarizable continuum model (PCM). DFT/PCM calculations of sodium D line specific rotations, [α]D, have been carried out for seven conformationally rigid chiral organic molecules (fenchone, camphor, α-pinene, β-pinene, camphorquinone, verbenone, and methyloxirane) for a diverse set of seven solvents (cyclohexane, carbon tetrachloride, benzene, chloroform, acetone, methanol, and acetonitrile). The predicted variation in [α]D for the solvents…