Enantiomorphing Chiral Plasmonic Nanostructures: A Counterintuitive Sign Reversal of the Nonlinear Circular Dichroism

Plasmonic nanostructures have demonstrated a remarkable ability to control light in ways never observed in nature, as the optical response is closely linked to their flexible geometric design. Due to lack of mirror symmetry, chiral nanostructures allow twisted electric field “hotspots” to form at the material surface. These hotspots depend strongly on the optical wavelength and nanostructure geometry. Understanding the properties of these chiral hotspots is crucial for their applications; for instance, in enhancing the optical interactions with chiral molecules. Here, the results of an elegant experiment are presented: by designing 35 intermediate geometries, the structure is “enantiomorphed” from one handedness to the other, passing through an achiral geometry. Nonlinear multiphoton microscopy is used to demonstrate a new kind of double‐bisignate circular dichroism due to enantiomorphing, rather than wavelength change. From group theory, a fundamental origin of this plasmonic chiroptical response is proposed. The analysis allows the optimization of plasmonic chiroptical materials. Contrary to what is possible with molecules, modern nanofabrication techniques allow the dimensions of chiral nanostructures to be finely tuned, morphing from one handedness to another (enantiomorphing). In addition, multiple enantiomorphing paths are possible, by varying different structure dimensions. Upon exploring such paths, counterintuitive chiral optical behavior can be revealed.