Chirality Discriminated by Heterodyne-Detected Vibrational Sum Frequency Generation

We first demonstrated chiral vibrational sum frequency generation (VSFG) in the heterodyne detection, which enables us to uniquely determine chiral second-order nonlinear susceptibility consisting of phase and amplitude and distinguish molecular chirality with high sensitivity. Liquid limonene was measured to evaluate the heterodyne-detected chiral VSFG developed in this study. <i>R</i>-(+)- and <i>S</i>-(−)-limonene showed clearly opposite signs in the complex spectra of the second-order nonlinear susceptibility in the CH stretching region. This is the first report of the chiral distinction by VSFG without any a priori knowledge about chiral and achiral spectral response. Furthermore, from the phase of the chiral VSFG field measured in the heterodyne detection, the origin of the chiral signal was ascribed to the bulk limonene. The heterodyne detection also improves detection limits significantly, allowing us to observe weak chiral signals in reflection. The heterodyne-detected chiral VSFG can provide information on absolute molecular configuration