Molecular Origins of the Remarkable Chiral Sensitivity of Second-Order Nonlinear Optics

Recent observations of remarkably large chiroptical effects in second‐harmonic generation (SHG) and sum‐frequency generation (SFG) measurements suggest exciting possibilities for the development of new chiral‐specific spectroscopies and novel chiral materials for nonlinear optics. Several fundamental studies designed to elucidate the molecular and macromolecular origins of the chiral responses are reviewed to provide a framework for development of this emerging field. In general, the chiral activity in SHG and SFG has the potential to arise from complex interactions between hosts of different competing effects. Fortunately, relatively simple electric dipole‐allowed mechanisms routinely dominate the nonlinear optical chiral activities of most practical systemsexpressions can often be generated to link the . This substantial reduction in complexity allows for the development of simple models connecting the macroscopic nonlinear optical response to intuitive molecular and supramolecular properties. Chirality goes simple: The molecular and macromolecular origins of the remarkable chiral responses in second harmonic generation and sum‐frequency generation (see graphic) are discussed. Although the chiral activity originates from a potentially complex array of interactions, remarkably simple physical models often capture the essence of the driving interactions.