We deconvolute the distinct and sometimes competing effects of geometric and material chirality in metastructures created from materials that are intrinsically chiral. We find that overlapping Mie-like resonances in nanodisk arrays leads to 6-fold CD enhancement compared to a uniform film. Furthermore, making the medium chiral does not necessarily increase CD; enhancement depends on the magnitude of the Pasteur parameter and its real and imaginary components. Finally, to demonstrate how geometric and material chirality can be combined, we design a geometrically chiral meta-atom out of chiral media and observe over 9-fold enhancement in both CD andg-factor compared to a metasurface comprised of achiral material.
more »
« less
Enhancing circular dichroism by chiral hotspots in silicon nanocube dimers
Circular dichroism (CD) spectroscopy, which measures the differential absorption of circularly polarized light with opposite handedness, is an important technique to detect and identify chiral molecules in chemistry, biology and life sciences. However, CD signals are normally very small due to the intrinsically weak chirality of molecules. Here we theoretically investigate the generation of chiral hotspots in silicon nanocube dimers for CD enhancement. Up to 15-fold enhancement of the global optical chirality is obtained in the dimer gap, which boosts the CD signal by one order of magnitude without reducing the dissymmetry factor. This chiral hotspot originates from the simultaneous enhancement of magnetic and electric fields and their proper spatial overlap. Our findings could lead to integrated devices for CD spectroscopy, enantioselective sensing, sorting and synthesis.
more »
« less
- Award ID(s):
- 1654192
- PAR ID:
- 10058263
- Date Published:
- Journal Name:
- Nanoscale
- Volume:
- 10
- Issue:
- 18
- ISSN:
- 2040-3364
- Page Range / eLocation ID:
- 8779 to 8786
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Detection and identification of chiral molecules are important for pharmaceutical industry, clinical analysis, and food analysis. Here, chiral molecular sensing based on spatially selective coupling between achiral metasurface and chiral molecules is demonstrated. The designed achiral metasurface exhibits strong optical chirality and electric field with dissymmetric distribution, and chiral molecules are selectively placed over the area with large optical chirality to form the coupled metasurface-molecule system with circular dichroism (CD) response for chiral molecular sensing. The CD spectra of the metasurface coupled with pure D-alanine enantiomer, L-alanine enantiomer and their mixtures are examined. The linear relationship between the peak CD value and the enantiomeric excess is demonstrated for the detection and identification of pure enantiomers and their mixtures. Furthermore, the CD response of the coupled system shows potential for the sensing of molar concentration of chiral molecules. Moreover, the effect of spatial location of molecules on the CD response is analyzed to show potential for position sensing of chiral molecules. These results of chiral molecular sensing with achiral metasurface offer new opportunities for advancing biomolecular sensing applications.more » « less
-
Achiral metasurfaces with near-field optical chirality have attracted great attention in molecular sensing and chiral emission control. Here, the circular dichroism (CD) response of an achiral metasurface induced by spatially selective coupling with polymethyl methacrylate (PMMA) molecules is demonstrated. A designed achiral metasurface with a V-shaped resonator exhibits large optical chirality with a strongly dissymmetric distribution under circular polarization. By introducing a PMMA molecule layer on top of the metasurface, which covers the area with large optical chirality, CD in absorption of 0.38 and a dissymmetric factor of optical chiralitygcof 0.16 are obtained. Furthermore, an analysis of the coupled harmonic oscillator model reveals stronger coupling strength between the PMMA layer and the metasurface under RCP incidence, compared to the LCP case. Moreover, it is shown that the far-field CD response of the metasurface is linearly correlated with the dissymmetric near-field optical chirality distribution. The demonstrated results present the potential for advancing applications in chiral molecule vibrational sensing, thermal emission control, and infrared chiral imaging.more » « less
-
Core-resonant circular dichroism (CD) signals are induced by molecular chirality and vanish for achiral molecules and racemic mixtures. The highly localized nature of core excitations makes them ideal probes of local chirality within molecules. Simulations of the circular dichroism spectra of several molecular families illustrate how these signals vary with the electronic coupling to substitution groups, the distance between the X-ray chromophore and the chiral center, geometry, and chemical structure. Clear insight into the molecular structure is obtained through analysis of the X-ray CD spectra.more » « less
-
We have synthesized inherently chiral cesium lead halide perovskite magic-sized clusters (PMSCs) and ligand-assisted metal halide molecular clusters (MHMCs) using the achiral ligands octanoic acid (OCA) and octylamine (OCAm). UV–vis electronic absorption was used to confirm characteristic absorption bands while circular dichroism (CD) spectroscopy was utilized to determine their chiroptical activity in the 412–419 and 395–405 nm regions, respectively. In contrast, the larger sized counterpart of PMSCs, namely, perovskite quantum dots (PQDs), do not show chirality. The inherent chirality of the clusters is tentatively attributed to a twisted chiral layered structure, defect-induced chiral structure, or twisted Pb–Br octahedramore » « less
An official website of the United States government

