Hyper-Rayleigh Scattering and Third-Harmonic Scattering in Chiral Liquids: Basic Evidences and Differences with Linear Chiroptical Techniques

Nonlinear chiroptical methods like hyper-Rayleigh optical activity (HROA) and third-harmonic optical activity (THOA) have a great potential in characterizing structure-chiroptical properties of molecular systems. Here, with these methods, we bring for the first time experimental and theoretical evidence of nonlinear chiroptical differences between enantiomers of simple chiral molecules, using exclusively linearly polarized incident light. The origin of these unexpected nonlinear chiroptical contributions comes from a new nonlinear source term of the form βOA(∇×μ(nω)), which is a bilinear coupling term including the linear chirality parameter, βOA, and the curl of the nonlinear induced electric dipole moment, μ(nω), both involving dipolar magnetic interactions. Through a simple nonlinear chiroptical model that we propose, we show that specific nonlinear chiroptical parameters can be quantified, thus bringing new insights into stereochemical and electronic structural features of molecular and supramolecular systems.