Two Spectroscopies in One: Interference of Circular Dichroism and Raman Optical Activity

Previously, we and other laboratories have reported an unusual and strong Raman optical activity (ROA) induced in solvents by chiral dyes. Various theories of the phenomenon appeared, but they were not capable of explaining fully the observed ROA band signs and intensities. In this work, an analysis based both on the light scattering theory and dedicated experiments provides a more complete understanding. For example, double‐cell magnetic circular dichroism and magnetic ROA experiments with copper‐porphyrin complex show that the induced chirality is observed without any contact of the solvents with the complex. The results thus indicate that a combination of electronic circular dichroism (ECD) with the polarized Raman scattering is responsible for the effect. The degree of circularity of solvent vibrational bands is a principal molecular property participating in the event. The insight and the possibility to predict the chirality transfer promise future applications in spectroscopy, chemical analysis and polarized imaging.
In a series of experiments and by a theoretical analysis we decipher Raman optical activity induced in achiral solvents as an interference of two phenomena, circular dichroism and polarized Raman scattering. Applications of this strong effect can be potentially found in analytical chemistry, spectroscopy, and imaging of biologically relevant systems.