Circularly Polarized Stimulated Emission from a Chiral Cavity Based on Apparent Circular Dichroism Organic Thin-Films
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Giant Apparent Optical Circular Dichroism in Thin Films of Bismuth-Based Hybrid Organic-Inorganic Metal Halide Semiconductor Through Preferred Orientation
Introducing chirality into organic/inorganic hybrid materials can impart chiroptical properties such as circular dichroism. The ability to tune chiroptical properties in self-assembled materials can have important implications for spintronic and optoelectronic applications. Here, a chiral organic cation, (R/S)-4-methoxy-a-methylbenzylammonium, is incorporated to synthesize the bismuth-based hybrid organic-inorganic metal halide semiconductor, (R/S-MeOMePMA)BiI4. Thin films of this Bi-based compound demonstrate large chiroptical responses, with circular dichroism anisotropy (gCD) values up to ˜0.1, close to the highest value observed in another chiral metal-halide semiconductor, (R-MBA2CuCl4). Detailed investigation reveals that this large gCD in (R/S-MeOMePMA)BiI4 is caused by the apparent CD effect. Careful selection of deposition conditions and the concomitant thin-film orientation enables the control of gCD, with maximum value observed when its thin film has a well-crystallized preferred (001) orientation parallel to the substrate. The results support a growing body of evidence that low symmetry plays an important role in achieving unusually large gCD in these chiral metal-halide materials and provides design rules for achieving large chiroptical response via morphology control.
chiroptic response↗
Quantum Enhanced Probes of Magnetic Circular Dichroism
Magneto-optical microscopies, including optical measurements of magnetic circular dichroism, are increasingly ubiquitous tools for probing spin-orbit coupling, charge-carrier g-factors, and chiral excitations in matter, but the minimum detectable signal in classical magnetic circular dichroism measurements is fundamentally limited by the shot-noise limit of the optical readout field. Here, a two-mode squeezed light source is used to improve the minimum detectable signal in magnetic circular dichroism measurements by 3 decibels compared with state-of-the-art classical measurements, even with relatively lossy samples like terbium gallium garnet. Furthermore, these results provide a framework for new quantum-enhanced magneto-optical microscopies that are particularly critical for environmentally sensitive materials and for low temperature measurements where increased optical power can introduce unacceptable thermal perturbations.
42 ENGINEERING↗
Deconstructing Chirality: Probing Local and Nonlocal Effects in Azobenzene Derivatives with X-ray Circular Dichroism
Resolving molecular chirality on the atomic scale remains a critical challenge in chemistry. Conventional Optical Circular Dichroism spectroscopy often overlooks subtle and localized structural features. Here, we computationally investigate site-specific X-ray circular dichroism (XCD) across a series of trans-azobenzene derivatives to deconstruct and interpret chiroptical signals at the atomic level. Our modeling reveals that XCD is capable of distinguishing dichroic contributions arising from both a local chiral center and a global molecular twist, revealing their intricate interplay and potential for constructive or destructive interference. We show that sterically induced global distortions can dominate the XCD signal in some cases, even suppressing the response from the chiral center itself. This insight suggests a new molecular design principle for tuning the chiroptical activity, which we extend by proposing strategies to achieve unidirectional photoisomerization through steric gearing. Altogether, this work establishes a quantitative framework for engineering chiroptical responses, laying the foundation for the design of functional chiral systems utilizing principles of unidirectional molecular motor-like conformational dynamics.
X-ray spectroscopy↗
A 2D chiral microcavity based on apparent circular dichroism
Abstract Engineering asymmetric transmission between left-handed and right-handed circularly polarized light in planar Fabry–Pérot (FP) microcavities would enable a variety of chiral light-matter phenomena, with applications in spintronics, polaritonics, and chiral lasing. Such symmetry breaking, however, generally requires Faraday rotators or nanofabricated polarization-preserving mirrors. We present a simple solution requiring no nanofabrication to induce asymmetric transmission in FP microcavities, preserving low mode volumes by embedding organic thin films exhibiting apparent circular dichroism (ACD); an optical phenomenon based on 2D chirality. Importantly, ACD interactions are opposite for counter-propagating light. Consequently, we demonstrated asymmetric transmission of cavity modes over an order of magnitude larger than that of the isolated thin film. Through circular dichroism spectroscopy, Mueller matrix ellipsometry, and simulation using theoretical scattering matrix methods, we characterize the spatial, spectral, and angular chiroptical responses of this 2D chiral microcavity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
X-ray and Optical Circular Dichroism as Local and Global Ultrafast Chiral Probes of [12]Helicene Racemization
Optical circular dichroism (OCD) is a well-established technique for probing molecular chirality typically in the UV-visible window. Although molecular chirality is usually related to a chiral center, it can alternatively describe a global structure. The electronic transitions are then delocalized and OCD is said to probe the global chirality. Recent advances controlling the polarization and spatial structure of X-ray beams have led to novel spectroscopic techniques such as X-ray circular dichroism (XCD), which can exploit the localized nature of the X-ray electronic transitions. XCD is thus sensitive to local structures and the relevant chirality probed with it can be referred as local. Here, we use the racemization mechanism of the [12]Helicene as a model to assess the capabilities of OCD and XCD as probes of global and local chiralities. In conclusion, our simulations suggest that XCD is a reliable spectroscopic technique for probing the local chirality of molecules, suggesting the further development of this experimental technique.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Topological Circular Dichroism in Chiral Multifold Semimetals
Uncovering the physical contents of the nontrivial topology of quantum states is a critical problem in condensed matter physics. Here, we study the topological circular dichroism in chiral semimetals using linear response theory and first-principles calculations. We show that, when the low-energy spectrum respects emergent SO(3) rotational symmetry, topological circular dichroism is forbidden for Weyl fermions, and thus is unique to chiral multifold fermions. This is a result of the selection rule that is imposed by the emergent symmetry under the combination of particle-hole conjugation and spatial inversion. Using first-principles calculations, we predict that topological circular dichroism occurs in CoSi for photon energy below about 0.2 eV. In conclusion, our Letter demonstrates the existence of a response property of unconventional fermions that is fundamentally different from the response of Dirac and Weyl fermions, motivating further study to uncover other unique responses.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Continuum-electron interferometry for enhancement of photoelectron circular dichroism and measurement of bound, free, and mixed contributions to chiral response
We develop photoelectron interferometry based on laser-assisted extreme ultraviolet ionization for flexible and robust control of photoelectron circular dichroism in randomly oriented chiral molecules. A comb of XUV photons ionizes a sample of chiral molecules in the presence of a time-delayed infrared or visible laser pulse promoting interferences between components of the XUV-ionized photoelectron wave packet. In striking contrast to multicolor phase control schemes relying on pulse shaping techniques, the magnitude of the resulting chiral signal is here controlled by the time delay between the XUV and laser pulses. Furthermore, we show that the relative polarization configurations of the XUV and IR fields allow for disentangling the contributions of bound and continuum states to the chiral response. Our proposal provides a simple, robust, and versatile tool for the control of photoelectron circular dichroism and experimentally feasible protocol for probing the individual contributions of bound and continuum states to the photoelectron circular dichroism in a time-resolved manner.
atomic and molecular processes in external fields↗
X-ray circular dichroism measured by cross-polarization x-ray transient grating
Measuring natural circular dichroism in the x-ray regime to extract stereochemical information from chiral molecules in solution remains a challenge. This is primarily due to technical limitations of the existing synchrotron sources, which hinder access to measurements of local chirality by exploiting core hole electronic transitions. In response to this challenge, we propose an alternative approach: utilizing XFEL-based cross-polarization x-ray transient grating (XTG). This method provides an indirect means to measure x-ray circular dichroism (XCD). Notably, our findings reveal that the signal emerges only once the excited cores have undergone dephasing through relaxation. XTG is now routinely measured in the XUV regime and has recently been made available for hard x-rays. Free electron lasers now offer polarization controls, and XTG can be extended to various polarization states for the two pump beams, making XCD measured by XTG feasible with the current state-of-the-art technology.
74 ATOMIC AND MOLECULAR PHYSICS↗
Large exchange-driven intrinsic circular dichroism of a chiral 2D hybrid perovskite
Abstract In two-dimensional chiral metal-halide perovskites, chiral organic spacers endow structural and optical chirality to the metal-halide sublattice, enabling exquisite control of light, charge, and electron spin. The chiroptical properties of metal-halide perovskites have been measured by transmissive circular dichroism spectroscopy, which necessitates thin-film samples. Here, by developing a reflection-based approach, we characterize the intrinsic, circular polarization-dependent complex refractive index for a prototypical two-dimensional chiral lead-bromide perovskite and report large circular dichroism for single crystals. Comparison with ab initio theory reveals the large circular dichroism arises from the inorganic sublattice rather than the chiral ligand and is an excitonic phenomenon driven by electron-hole exchange interactions, which breaks the degeneracy of transitions between Rashba-Dresselhaus-split bands, resulting in a Cotton effect. Our study suggests that previous data for spin-coated films largely underestimate the optical chirality and provides quantitative insights into the intrinsic optical properties of chiral perovskites for chiroptical and spintronic applications.
25 ENERGY STORAGE↗
Ligand-Induced Size-Dependent Circular Dichroism in Quantum Dots
Recent experiments have probed the chiral properties of semiconductor nanocrystal (NC) quantum dots (QDs), but understanding the circular dichroism line shape, excitonic features, and chirality induction mechanism remains a challenge. We propose an atomistic pseudopotential method to model chiral ligand passivated QDs, computing circular dichroism (CD) spectra for CdSe QDs (2.6-3.8 nm). We find strong agreement between calculated and measured line shapes, predicting consistent bisignate line shapes with decreasing CD magnitude as size increases. Further, our analysis reveals the origin of bisignate line shapes, arising from nondegenerate excitons with opposing angular momenta. We also explore the impact of chiral ligand orientation on QD surfaces, observing changes in the optical activity magnitude and sign. This orientation sensitivity offers the means to distinguish ordered from disordered ligand configurations, facilitating the study of order-disorder transitions at ligand-QD interfaces.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Highly Elliptic Circular Dichroism of Copper Aspartate One-Dimensional Nanostructures across the Ultraviolet to Terahertz Ranges
Since the discovery of chirality, circular dichroism (CD) of mirror-asymmetric molecules has been studied across the ultraviolet, visible, and near-infrared ranges. Recently, chiroptical activity studies have expanded to the terahertz (THz) range, where resonance peaks originate from collective vibrations of tens and hundreds of atoms. Here, in this study, we synthesized Cu 2+ coordination complexes with L- and D-aspartic acid as nanowires and nanorods and characterized their chiroptical activity across multiple frequency ranges. Both chiral nanostructures exhibit strong electronic CD (ECD), primarily from Cu 2+ d-d transitions, while vibrational CD (VCD) spectra show sharp C=O, C–H, and O–H vibronic peaks, indicating higher atomic defect densities in nanorods than nanowires. Although THz CD (TCD) spectra are broad, they exhibit ∼1000× greater ellipticity than ECD and VCD, perhaps warranting previous references to circular dichroism of nanostructures as giant. Comparative TCD analysis highlights strong chiral phonon sensitivity, underscoring its potential for probing defect densities and structural changes for various chiral nanostructures and (bio)crystals.
THz spectroscopy↗
Replication Data for: Deconstructing Chirality: Probing Local and Non-local Effects in Azobenzene Derivatives with X-ray Circular Dichroism
Resolving molecular chirality at the atomic scale remains a critical challenge in chemistry. Conventional Optical Circular Dichroism spectroscopy often overlooks subtle and localized structural features. Here, we computationally investigate site-specific X-ray Circular Dichroism (XCD) across a series of trans-azobenzene derivatives to deconstruct and interpret chiroptical signals at the atomic level. Our modeling reveals that XCD is capable of distinguishing dichroic contributions arising from both a local chiral center and global molecular twist, revealing their intricate interplay and potential for constructive or destructive interference. We show that sterically-induced global distortions can dominate the XCD signal in some cases, even suppressing the response from the chiral center itself. This insight suggests a new molecular design principle for tuning chiroptical activity, which we extend by proposing strategies to achieve unidirectional photoisomerization through steric gearing. Altogether, this work establishes a quantitative framework for engineering chiroptical responses, laying the foundation for the design of functional chiral systems utilizing principles of unidirectional molecular motor-like conformational dynamics.
Chemistry↗
Emergence of a Low-Energy Peak in the Smoothed Absolute Value Circular Dichroism Spectra of Small Helical Gold Nanorods
We calculate, using time-dependent density functional theory, absorption and circular dichroism (CD) spectra for a series of small helical gold nanorod structures with a width of 0.6 nm and length increasing from 0.7 nm for Au 24 to 1.9 nm for Au 56 . For a low-energy window, ranging from 1.7 to 4.1 eV, broadening the lines in the absorption spectra results in a low energy peak which previous studies have identified as the (localized) plasmon resonance. As expected, the absorption peak position of the plasmon resonance systematically redshifts as the length of the nanorod increases. However, trends in the CD and straightforwardly broadened CD spectra are more difficult to discern. We introduce the idea of an absolute value CD spectrum and show that broadening the lines results in a low energy peak that has not previously been reported. The peak position systematically redshifts as the length of the nanorod increases but over a significantly smaller range than that for the absorption spectrum.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Three-dimensional dispersion in the type-II Dirac semimetals PtTe 2 and PdTe 2 revealed through circular dichroism in angle-resolved photoemission spectroscopy
PtTe 2 and PdTe 2 are among the first transition metal dichalcogenides that were predicted to host type-II Dirac fermions, exotic particles prohibited in free space. These materials are layered and air stable, which makes them top candidates for technological applications that take advantage of their anisotropic magnetotransport properties. Here, in this work, we provide a detailed characterization of the electronic structure of PtTe 2 and PdTe 2 using angle-resolved photoemission spectroscopy (ARPES) and density functional theory calculations, offering an alternative interpretation for one of the Dirac-like dispersions in these materials. Through the use of circularly polarized light, we report a different behavior of such dispersion in PdTe 2 compared to PtTe 2 , that we relate to a symmetry analysis of the dipole matrix element. Such analysis reveals a link between the observed circular dichroism and the different momentum-dependent terms in the dispersion of these two compounds, despite their close similarity in crystal structure. Additionally, our data show a clear difference in the circular dichroic signal for the type-II Dirac cones characteristic of these materials, compared to their topologically protected surface states. Our paper provides a useful reference for the ARPES characterization of other transition metal dichalcogenides with topological properties and illustrates the use of circular dichroism as a guide to identify the topological character and attributes of two otherwise equivalent band dispersions.
angle-resolved photoemission spectroscopy↗
Linear and Nonlinear X-ray Spectra of Chiral Molecules: X-ray Circular Dichroism, Sum- and Difference-Frequency Generation of Fenchone and Cysteine
Recent advancements in X-ray light sources enable element-sensitive nonlinear spectroscopies for probing molecular chirality. We simulate X-ray absorption spectroscopy, X-ray circular dichroism (XCD), and nonlinear optical/X-ray SFG and DFG (OX SFG/DFG) signals for two prototypical chiral molecules, fenchone and cysteine. Furthermore, our multireference simulations reproduce experimental data and reveal how novel X-ray spectroscopies exploit the site- and element-sensitivity of X-rays to uncover molecular asymmetry. The XCD spectra show strong asymmetries at chiral centers, while distant atoms contribute weaker signals. The OX SFG/DFG signals, under fixed resonant optical excitation, strongly depend on the core and valence excitations. This allows us to introduce two-dimensional (2D) chirality-sensitive valence-core spectroscopy, which provides insight into the overlap between valence orbitals and local molecular asymmetry. Finally, our estimates using realistic laser and X-ray pulse parameters demonstrate that such nonlinear experiments are feasible at XFELs, offering a promising tool for investigating chiral molecules.
Circular dichroism spectroscopy↗
Theory predicts 2D chiral polaritons based on achiral Fabry–Pérot cavities using apparent circular dichroism
Abstract Realizing polariton states with high levels of chirality offers exciting prospects for quantum information, sensing, and lasing applications. Such chirality must emanate from either the involved optical resonators or the quantum emitters. Here, we theoretically demonstrate a rare opportunity for realizing polaritons with so-called 2D chirality by strong coupling of the optical modes of (high finesse) achiral Fabry–Pérot cavities with samples exhibiting “apparent circular dichroism” (ACD). ACD is a phenomenon resulting from an interference between linear birefringence and dichroic interactions. By introducing a quantum electrodynamical theory of ACD, we identify the design rules based on which 2D chiral polaritons can be produced, and their chirality can be optimized.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Control over Banded Morphologies and Circular Dichroism in Chiral Halide Perovskites
Chiral halide perovskites (c-HPs) merge the chirality of organic cations with the semiconducting properties of metal halide frameworks, creating a family of chiral semiconductors with tunable chiroptoelectronic behavior. Here, we describe the impact of periodic banded morphologies of textured c-HP ( R/S -NEA) 2 PbBr 4 films (NEA = 1- (1-naphthyl)ethylammonium) on their chiroptical behavior. Due to the interplay between the crystalline and glassy phases, the c-HP film growth is driven by rhythmic precipitation, producing a distinctive controllable radial banded pattern with the ( R/S -NEA) 2 PbBr 4 inorganic planes oriented parallel to the substrate. The banded morphology can be controlled, as evidenced by the growth temperature dictating the ridge-to-ridge spacing as well as the density of banded regions. The resulting circular dichroism (CD) spectral shape, intensity, and polarity vary in a seemingly random manner across processing conditions. However, these spectral features can be explained by considering key features of the banded morphology, such as refraction of the incident light due to surface morphology, birefringence, and stacked, rotated crystallites. These effects cannot be canceled by averaging front and back CD spectra of c-HP films, and our model incorporating these effects reproduces all observed CD spectra remarkably well. The control over the c-HP morphology and prediction capabilities of our CD modeling leads to further understanding of this class of semiconductors and the possibility of exploiting structural features for light polarization control akin to enhanced metamaterials.
14 SOLAR ENERGY↗