Principles of enantio-selective excitation in three-wave mixing spectroscopy of chiral molecules

Abstract

Three-wave mixing spectroscopy of chiral molecules, which exist in left-handed and right-handed conformations, allows for enantio-selective population transfer despite random orientation of the molecules. This is based on constructive interference of the three-photon pathways for one enantiomer and destructive one for the other. We prove here that three mutually orthogonal polarization directions are required to this end. Two different dynamical regimes exist to realize enantio-selective population transfer, and we show that they correspond to different phase conditions in the three-wave mixing. We find the excitation scheme used in current rotational three-wave mixing experiments of chiral molecules with $C_1$ symmetry to be close to optimal and discuss prospects for ro-vibrational three-wave mixing experiments of axially chiral molecules. Our comprehensive study allows us to clarify earlier misconceptions in the literature.

31 pages, 11 figures

References in corpus (6)

• Enantiomer-Specific State Transfer of Chiral Molecules
• Generalized Stern-Gerlach Effect for Chiral Molecules
• Optically-Induced Highly-Efficient Detection and Separation of Chiral Molecules through Shortcuts to Adiabaticity
• Dynamic method to distinguish between left- and right-handed chiral molecules
• Rovibrational cooling of molecules by optical pumping
• Effect of molecular rotation on enantioseparation

Cited by in corpus (5)

• Enantioselective Orientation of Chiral Molecules Induced by Terahertz Pulses with Twisted Polarization
• Composite pulses for high fidelity population transfer in three-level systems
• Rational pulse design for enantiomer-selective microwave three-wave mixing
• Orientation Echoes via Concerted Terahertz and Near-IR excitation
• Quantitative study of enantiomer-specific state transfer