scholarly journals Tunable circular dichroism through absorption in coupled optical modes of twisted triskelia nanostructures

2022 ◽  
Vol 12 (1) ◽  
Author(s):  
Javier Rodríguez-Álvarez ◽  
Antonio García-Martín ◽  
Arantxa Fraile Rodríguez ◽  
Xavier Batlle ◽  
Amílcar Labarta

AbstractWe present a system consisting of two stacked chiral plasmonic nanoelements, so-called triskelia, that exhibits a high degree of circular dichroism. The optical modes arising from the interactions between the two elements are the main responsible for the dichroic signal. Their excitation in the absorption cross section is favored when the circular polarization of the light is opposite to the helicity of the system, so that an intense near-field distribution with 3D character is excited between the two triskelia, which in turn causes the dichroic response. Therefore, the stacking, in itself, provides a simple way to tune both the value of the circular dichroism, up to 60%, and its spectral distribution in the visible and near infrared range. We show how these interaction-driven modes can be controlled by finely tuning the distance and the relative twist angle between the triskelia, yielding maximum values of the dichroism at 20° and 100° for left- and right-handed circularly polarized light, respectively. Despite the three-fold symmetry of the elements, these two situations are not completely equivalent since the interplay between the handedness of the stack and the chirality of each single element breaks the symmetry between clockwise and anticlockwise rotation angles around 0°. This reveals the occurrence of clear helicity-dependent resonances. The proposed structure can be thus finely tuned to tailor the dichroic signal for applications at will, such as highly efficient helicity-sensitive surface spectroscopies or single-photon polarization detectors, among others.

Science ◽  
2020 ◽  
Vol 368 (6498) ◽  
pp. 1465-1468 ◽  
Author(s):  
Steven Daly ◽  
Frédéric Rosu ◽  
Valérie Gabelica

DNA and proteins are chiral: Their three-dimensional structures cannot be superimposed with their mirror images. Circular dichroism spectroscopy is widely used to characterize chiral compounds, but data interpretation is difficult in the case of mixtures. We recorded the electronic circular dichroism spectra of DNA helices separated in a mass spectrometer. We studied guanine-rich strands having various secondary structures, electrosprayed them as negative ions, irradiated them with an ultraviolet nanosecond optical parametric oscillator laser, and measured the difference in electron photodetachment efficiency between left and right circularly polarized light. The reconstructed circular dichroism ion spectra resembled those of their solution-phase counterparts, thereby allowing us to assign the DNA helical topology. The ability to measure circular dichroism directly on biomolecular ions expands the capabilities of mass spectrometry for structural analysis.


2021 ◽  
Author(s):  
Chen Fang ◽  
Qing Chai ◽  
Ye Chen ◽  
Yan Xing ◽  
Zai-fa Zhou

Abstract Optical metamaterials are widely used in electromagnetic wave modulation due to their sub-wavelength feature sizes. In this paper, a method to plate an achiral nanopillar array with chiral coating by the secondary effect in focused ion beam induced deposition is proposed. Guided by the pattern defined in a bitmap with variable residence time, the beam scan strategy suppresses the interaction between adjacent nanostructures. A uniform chiral coating is formed on the target nanostructure without affecting the adjacent nanostructure, under carefully selected beam parameters and the rotation angle of the sample stage. Energy Dispersive X-Ray Spectroscopy results show that the chiral film has high purity metal, which enables the generation of localized surface plasmon resonances and causes the circular dichroism under circularly polarized light illumination. Finally, the tailorable circular dichroism spectrum of the coated array is verified by the Finite Difference Time Domain method.


1994 ◽  
Vol 48 (2) ◽  
pp. 167-175 ◽  
Author(s):  
Lei Geng ◽  
Linda B. McGown

A major difficulty in fluorescence-detected circular dichroism (FDCD) and lifetime-resolved fluorescence-detected circular dichroism (LRFDCD) is the generation of equal excitation intensities of left circularly polarized light (LCPL) and right circularly polarized light (RCPL). In the presence of unequal intensities, the observed FDCD signal of an optically active sample, or the resolved FDCD signals of a multicomponent system in the case of LRFDCD, will be contaminated by a factor that is the ratio of the two unequal intensities. For optically inactive samples, a sample-independent, artifactual, nonzero signal of constant magnitude is observed. A general scheme is presented for the correction of these inaccuracies caused by unequal intensities of LCPL and RCPL. Large differences between LCPL and RCPL excitation intensities were artificially introduced in steady-state FDCD measurements, and the artifact was accurately corrected by the scheme. Corrected results for the different experimental approaches that have been described for LRFDCD showed similarly good accuracy. In a related consideration, inclusion of the total absorbance and absorption circular dichroism of the sample in the calculation of the FDCD signal is shown to be essential for samples with high absorbances.


2013 ◽  
Vol 59 ◽  
pp. 359-382 ◽  
Author(s):  
Andrew J. Thomson ◽  
Laurence D. Barron

Philip J. Stephens was a theoretical chemist who brought to fruition two new forms of optical spectroscopy, using circularly polarized light, for the determination of electronic structure and molecular stereochemistry. The first was magnetic circular dichroism (MCD), the wavelength dependence of the differential absorption of left and right circularly polarized light induced by a magnetic field applied parallel to the light beam. Stephens established a methodology for extracting from MCD spectra the angular momentum characteristics of ground and excited electronic states and demonstrated applications to the assignment of the optical spectra of coordination complexes of transition metals and to metalloproteins. In the second half of his career Stephens led the field of vibrational circular dichroism (VCD), the measurement of the natural circular dichroism (CD) arising from the vibrational transitions of chiral molecules. He developed instrumental techniques to measure this weak dichroism over a wide frequency range with high sensitivity. Subsequently he developed a quantum-mechanical method that yielded reliable calculations of VCD spectra by using density functional theory. Thus absolute configurations of all the chiral centres in an organic molecule are readily established. Given the increasing importance of enantiomerically pure chiral drugs, VCD has found widespread application in the pharmaceutical industry. Philip had not only a deep understanding of chemical theory but also a thorough grasp of experiments. His lectures on theoretical topics were models of clarity. He was also an accomplished pianist in demand, when a student at Oxford University, as an accompanist and for chamber concerts.


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