Electromagnetic Enantiomer: Chiral Nanophotonic Cavities for Inducing Chemical Asymmetry.

Chiral molecules, a cornerstone of chemical sciences with applications ranging from pharmaceuticals to molecular electronics, come in mirror-image pairs called enantiomers. However, their synthesis often requires complex control of their molecular geometry. We propose a strategy called "electromagnetic enantiomers" for inducing chirality in molecules located within engineered nanocavities using light, eliminating the need for intricate molecular design. This approach works by exploiting the strong coupling between a nonchiral molecule and a chiral mode within a nanocavity. We provide evidence for this strong coupling through angular emission patterns verified by numerical simulations and with complementary evidence provided by luminescence lifetime measurements. In simpler terms, our hypothesis suggests that chiral properties can be conveyed on to a molecule with a suitable chromophore by placing it within a specially designed chiral nanocavity that is significantly larger (hundreds of nanometers) than the molecule itself. To demonstrate this concept, we showcase an application in display technology, achieving efficient emission of circularly polarized light from a nonchiral molecule. The electromagnetic enantiomer concept offers a simpler approach to chiral control, potentially opening doors for asymmetric synthesis.

Rapid modulation of left- and right-handed optical vortices for precise measurements of helical dichroism.

Helical dichroism (HD), which is defined as the difference in optical absorption between chiral pairs of lights involving left-handed (LH) and right-handed (RH) optical vortices (OVs) carrying orbital angular momentum (OAM), is a promising way to characterize chiral materials. In the current major methods of OV generation using spatial light modulators (SLMs), the speed of OAM switching is typically as slow as 100 Hz, which is comparable to low-frequency noise, making precise chiral detection difficult. Here, we theoretically propose and experimentally demonstrate a rapid modulation of the LH and RH OVs at around 50 kHz. This modulation is achieved through a rapid modulation of circularly polarized lights carrying spin angular momentum (SAM), combined with a SAM-OAM conversion technique. We establish a theory not only for rapid OV modulation but also for HD measurements using the modulated OVs. We experimentally verify the theory using helical phase holograms drawn on a SLM as a pseudo-HD active sample. Our work addresses the limitations of current methods and offers a new avenue for precise HD measurements, paving the way for the development of sensitive chiral-optical spectroscopy techniques.

Circular dichroism of pseudo-two-dimensional metal nanostructures: Rotational symmetry and reciprocity.

Circular dichroism (CD) spectra for pseudo-two-dimensional chiral nanomaterials were systematically investigated and analyzed in relation to the rotational symmetry of the nanomaterials. Theoretically, an ideal two-dimensional chiral matter is CD inactive for light incident normal to the plane if it possesses threefold or higher rotational symmetry. If the matter has two- or onefold rotational symmetry, it should exhibit CD activity, and the CD signal measured from the back side of the matter is expected to be inverted from that measured from the front side. For pseudo-two-dimensional chiral gold nanostructures fabricated on glass substrates using electron beam lithography, matter with fourfold rotational symmetry is found to be CD active, even when special care is taken to ensure that the optical environments for the front and back sides of the sample are equivalent. In this case, the CD signal measured from the back side is found to be almost exactly the same as that measured from the front side. It is revealed that the observed chiro-optical behavior arises from three-dimensional chiral characteristics due to differences in the surface shape between the front and back sides of the structures. For matter that is two- or onefold rotationally symmetric, the CD signal measured from the back side is not coincident with that from the front side. For certain wavelength regions, the CD signals measured from the front side and back side are observed to be similar, while at other wavelengths, the inverted component of the CD signals is found to dominate. The observed CD spectral behavior for reciprocal optical measurement configurations is considered to be determined by a balance between the in-plane isotropic and anisotropic components of the chiral permittivity.