Sensing Chirality with Rotational Spectroscopy

Chiroptical spectroscopy techniques for the differentiation of enantiomers in the condensed phase are based on an established paradigm that relies on symmetry breaking using circularly polarized light. We review a novel approach for the study of chiral molecules in the gas phase using broadband rotational spectroscopy, namely microwave three-wave mixing, which is a coherent, nonlinear, and resonant process. This technique can be used to generate a coherent molecular rotational signal that can be detected in a manner similar to that in conventional Fourier transform microwave spectroscopy. The structure (and thermal distribution of conformations), handedness, and enantiomeric excess of gas-phase samples can be determined unambiguously by employing tailored microwave fields. We discuss the theoretical and experimental aspects of the method, the significance of the first demonstrations of the technique for enantiomer differentiation, and the method's rapid advance into a robust choice to study molecular chirality in the gas phase. Very recently, the microwave three-wave mixing approach was extended to enantiomer-selective population transfer, an important step toward spatial enantiomer separation on the fly.