Optical Chirality Determined from Mueller Matrices

Optical chirality, in terms of circular birefringence and circular dichroism, is described by its electromagnetic and magnetoelectric material tensors, and the corresponding optical activity contributes to the Mueller matrix. Here, spectroscopic ellipsometry in the spectral range 210–1690 nm is used to address chiral phenomena by measuring Mueller matrices in transmission. Three approaches to determine chirality parameters are discussed. In the first approach, applicable in the absence of linear polarization effects, circular birefringence and circular dichroism are evaluated directly from elements of a Mueller matrix. In the second method, differential decomposition is employed, which allows for the unique separation of chirality parameters from linear anisotropic parameters as well as from depolarization provided that the sample is homogeneous along the optical path. Finally, electromagnetic modeling using the Tellegen constitutive relations is presented. The last method also allows structural effects to be included. The three methods to quantify optical chirality are demonstrated for selected materials, including sugar solutions, α-quartz, liquid crystals, beetle cuticle, and films of cellulose nanocrystals.

Quantification of Optical Chirality in Cellulose Nanocrystal Films Prepared by Shear-Coating

Evaporation-induced-self-assembly is widely used to produce chiral cellulose nanocrystal (CNC) free-standing films reflecting left-handed polarized light. Research on supported chiral CNC films is rather scarce. The reflection and/or transmission of unpolarized light are the most common optical techniques used to characterize the selective reflection of CNC films whereas the use of techniques to quantify chiral properties is limited. Here, the fabrication of chiral CNC films supported on glass substrates by a shear-coating method, as well as a full characterization of their polarization properties, are reported. Optical chirality is evidenced in films, showing a brilliant blue structural color when viewed through a left-handed polarizer and darkness through a right-handed polarizer. Mueller-matrix data in the reflection and transmission modes are used to quantitatively characterize the structural origin of color in the films. The quantification of the linear and circular birefringence, as well as circular dichroism, is performed by analytical inversion of the Mueller matrix data in the transmission mode and regression analysis using Tellegen constitutive equations. The equivalence of the two methods to quantify the structural chirality in CNC films is demonstrated. The swelling of films in water and kinetics during drying is studied by reflection spectroscopy.

Enhancement of Optical Chirality Using Metasurfaces for Enantiomer-Selective Molecular Sensing

Circular dichroism (CD) is a physical property observed in chiral molecules by inducing the difference of absorption between left- and right-handed circularly polarized light (CPL). Circular dichroism spectroscopy is widely used in the field of chemistry and biology to distinguish the enantiomers, which typically show either positive or severe side effects in biological applications depending on the molecular structures’ chirality. To effectively detect the chirality of molecules, diverse designs of nanostructured platforms are proposed based on optical resonances that can enhance the optical chirality and amplify the signal of circular dichroism. However, the underlying physics between the optical chirality and the resonance in a nanostructure is largely unexplored, and thus designing rules for optimal chiral detection is still elusive. Here, we carry out an in-depth analysis of chiral enhancement (C enhancement) in nanostructured surfaces to find the relationship between optical resonances and chirality. Based on the relations, we optimize the nanostructured metasurface to induce effective chiral detection of enantiomers for diverse conditions of molecule distribution. We believe that the proposed designing rules and physics pave the important pathway to enhance the optical chirality for effective circular dichroism spectroscopy.

Orientation Averaging of Optical Chirality Near Nanoparticles and Aggregates

Artificial nanostructures enable fine control of electromagnetic fields at the nanoscale, a possibility that has recently been extended to the interaction between polarised light and chiral matter. The theoretical description of such interactions, and its application to the design of optimised structures for chiroptical spectroscopies, brings new challenges to the common set of tools used in nano-optics. In particular, chiroptical effects often depend crucially on the relative orientation of the scatterer and the incident light, but many experiments are performed with randomly-oriented scatterers, dispersed in a solution. We derive new expressions for the orientation-averaged local degree of optical chirality of the electromagnetic field in the presence of a nanoparticle aggregate. This is achieved using the superposition T -matrix framework, ideally suited for the derivation of efficient orientation-averaging formulas in light scattering problems. Our results are applied to a few model examples, and illustrate several non-intuitive aspects in the distribution of orientation-averaged degree of chirality around nanostructures. The results will be of significant interest for the study of nanoparticle assemblies designed to enhance chiroptical spectroscopies, and where the numerically-efficient computation of the averaged degree of optical chirality enables a more comprehensive exploration of the many possible nanostructures.