Engineering PapersSearch

SEARCH · Engineering Papers

Results for “chirality”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2

Symmetry Breaking Induced by Chiral Phosphonic Acids in a 2D Tin-Halide Perovskite

The ability to induce and modulate chirality in metal halide perovskite semiconductors (MHPs) using chiral additives expands the compositional design space and offers a means of tuning chiroptical properties. Motivated by the ability of phosphonic acids to interact with metal ions, we designed three chiral phosphonic acids (CPAs) to impose chirality in otherwise achiral 2D MHP, phenylammonium tin iodide (PA 2 SnI 4 ). We found that both the position of the phosphonic acid relative to the bond between the two naphthalene rings (i.e., the chiral axis) and the distance between the phosphonic acid and the binaphthyl chiral units significantly impact the transfer of structural chirality into the MHP lattice. The compound with a phosphonic acid directly bound to one of the naphthalene rings at the carbon adjacent to the chiral axis resulted in the largest circular dichroism dissymmetry factor of the three phosphonic acids. Furthermore, optical pump-terahertz probe measurements reveal an increase in the charge carrier mobility in the MHPs following the addition of CPAs. This dual functionality of CPAs in inducing chirality and improving charge transport properties in MHPs is promising for chiral-optoelectronic applications.

14 SOLAR ENERGY

Three-State Electrochiroptical Switches Derived from Chiral Stable Carbenes

Chiral redox switches have been used to develop stimuli-responsive materials and organic electronics wherein small molecule chirality produces new functionality. Despite the widespread use of stable carbenes in redox-active materials and asymmetric synthesis, their integration into chiral redox switches remains largely unexplored. Herein, we show that chiral stable carbenes can be used to construct helically chiral overcrowded alkenes which function as three-state electrochiroptical switches. Redox-driven (de)aromatization triggers the reversible exchange of helical and axial chirality via a helically chiral π-radical cation. Due to dramatic changes in both electronic and geometric structure, including the inversion of helical chirality, each state exhibits distinct chiroptical properties. As a proof of concept, we demonstrate multiple cycles of electrochemical ON–OFF switching and sign inversion of the electronic circular dichroism response. Overall, this work establishes chiral stable carbenes as promising building blocks for chiral and redox-switchable materials.

Chirality

Attosecond control and measurement of chiral photoionization dynamics

Many chirality-sensitive light–matter interactions are governed by chiral electron dynamics. Therefore, the development of advanced technologies making use of chiral phenomena would critically benefit from measuring and controlling chiral electron dynamics on their natural attosecond timescales. Such endeavours have so far been hampered by the lack of characterized circularly polarized attosecond pulses, an obstacle that has recently been overcome. Here we introduce chiroptical spectroscopy with attosecond pulses and demonstrate attosecond coherent control over photoelectron circular dichroism (PECD), as well as the measurement of chiral asymmetries in the forward–backward and angle-resolved photoionization delays of chiral molecules. We show that co-rotating attosecond and near-infrared (IR) pulses can nearly double the PECD and even change its sign compared with single-photon ionization. We demonstrate that chiral photoionization delays depend on both polar and azimuthal angles of photoemission in the light-propagation frame, requiring 3D momentum resolution. We measure forward–backward chiral-sensitive delays of up to 60 as and polar-angle-resolved photoionization delays of up to 240 as, which include an asymmetry of about 60 as originating from chirality in the continuum–continuum transitions. Attosecond chiroptical spectroscopy opens the door to quantitatively understanding and controlling the dynamics of chiral molecules on the electronic timescale.

Atomic and molecular interactions with photons

Chirality-Induced Spin Selectivity in Hybrid Organic-Inorganic Perovskite Semiconductors

The movement of charges through a chiral medium results in a spin-polarized charge current. This phenomenon, known as the chirality-induced spin selectivity (CISS) effect, enables control over spin populations without the need for magnetic components and operates at room temperature. CISS has been discovered in a range of chiral media and most prominently studied in chiral organic molecular species. Chiral hybrid organic-inorganic perovskite semiconductors combine the unique and functional aspects of inorganic semiconductors with chiral molecules. The inorganic component borrows the homochirality of the organic component to yield a unique family of highly tunable chiral semiconductors, where the enantiomeric purity is defined by the organic component. Semiconductors already form the backbone of modern-day technologies. Adding chirality and control over spin through CISS provides new avenues for creative technological development. This review is intended to be an introduction to these unique systems and the demonstrations of CISS and spin control.

14 SOLAR ENERGY

Can the chirality of the ISM be measured

Many moderately complex carbon-based molecules of the type associated with biological systems can exist in one of two mirror-image forms (left-handed and right-handed), which can be distinguished on the basis of their influence on the state of polarization of a light beam. Both forms are possible in nature; yet in living organisms it is invariably the rule that one of these two species predominates. This gives rise to a net chirality. One possible explanation for the net chirality is that the early earth was somehow seeded from the ISM with an excess of chiral organic compounds which led to the development of life forms which are based on left-handed amino acids and right-handed sugars. Molecular spectroscopy of the interstellar medium (ISM) has revealed a complex variety of molecular species similar to those thought to have been available in the oceans and atmospheres of the earth at the time life formed. The detection of such molecules demonstrates the generality of the chemical processes occurring in both environments. If this generality extends to the processes which produce chirality, it may be possible to detect a net chirality in the ISM. This is of particular interest because determining whether or not net chirality exists elsewhere in the universe is an essential aspect of understanding how life developed on earth and how widely distributed it might be. Researchers report preliminary results of a feasibility study to determine whether or not a net chirality in the ISM can be measured. If laboratory results identify candidate chiral molecules that might exist in the ISM, the next step in this feasibility study will be to estimate the detectability of the chiral signature in astrophysical environments.

Pendleton, Y.

Observation of Topological Chirality Switching Induced Freezing of a Skyrmion Crystal

Magnetic skyrmions are topologically protected quasi-particles with a well-defined chirality. Control over their chirality is proposed as an additional feature for encoding data bits or as qubits in quantum computing due to their high efficiency and stability against achiral magnetic textures. Here it is shown that an in-plane magnetic field can be utilized to reshape the energy barriers between different skyrmionic bubbles (e.g., Bloch type, type-II) enabling spontaneous chirality fluctuations with a frequency that increases with the strength of the in-plane field. The insulating van der Waals ferromagnet CrBr3 is used as an archetypal system for low damping, reduced energy dissipation and a high number of magnetic phases to capture the chirality dynamics in real time through cryo-Lorentz transmission electron microscopy. It is observed that the interplay between the intrinsic Dzyaloshinskii–Moriya interaction and out-of-plane field biased the chirality dynamics, favoring one handedness over the other. A remarkable consequence of the spontaneous chirality switching mechanism is that it induces a freezing (or crystallization) process in the skyrmion lattice. As the bubbles fluctuate between Bloch and type-II they elongate and shrink parallel to the in-plane field. Subsequently, the overall lattice crystallizes along the in-plane field direction, inducing a phase transition from a disordered liquid state to a hexatic phase where skyrmions are highly ordered resembling that of a solid. The results indicate chirality as an active element in the creation of topologically protected skyrmion crystals unveiling pathways toward chiral spintronic device platforms with tunable embedded configuration.

2D Phase Transition

Technical Routes to Achieve High Circular Polarized Luminescence in Chiral Perovskites: A Mini‐Review

Chiral hybrid organic-inorganic perovskites (HOIPs) have emerged as promising materials for optoelectronic and spintronic applications, leveraging unique properties such as circularly polarized luminescence (CPL), circularly polarized nonlinear optical (NLO) emission, and chiral-induced spin selectivity (CISS). However, challenges remain in stabilizing these materials under environmental stresses and precisely controlling chirality for scalable use. This review summarizes five main strategies to induce chirality in HOIPs, i.e., direct incorporation of chiral cations, surface modification with chiral ligands, ion doping, template-induced chirality, and chiral metasurfaces. Each approach offers distinct advantages for optimizing CPL efficiency and device stability, paving the way for next-generation applications in CPL detectors, information encryption, spintronic devices, etc.

14 SOLAR ENERGY

In-Situ Ligand-Induced Chirality Transfer in Emissive CdSe Nanoplatelets

Terminating semiconductor nanocrystals with chiral organic ligands can induce chiroptical properties that combine the chiral character of the ligands with the strong and tunable optical properties of the nanocrystal. However, the synthesis of such chiral-modified nanocrystals is currently limited by solvent incompatibility between polar chiral ligands and nonpolar traditional ligands, as well as by ligand dissolution behavior that ultimately compromises nanocrystal quality and the degree to which chiroptical properties can be manipulated. In this work, we demonstrate a single-step synthesis of chiral cadmium selenide (CdSe) nanoplatelets (NPLs) that eliminates the need for postsynthetic ligand exchange in aqueous solvents, resulting in highly emissive chiral CdSe NPLs. By directly incorporating chiral aminodecanoic acid ligands during synthesis, we achieve in situ ligand binding and chirality transfer to CdSe NPLs. This approach produces CdSe NPLs with high photoluminescence quantum efficiencies of 50% and circular dichroism dissymmetry factors (gCD) on the order of 10 –4 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Detection of chiral spin fluctuations driven by frustration in Mott insulators

Topologically ordered states, such as chiral spin liquids, have been proposed as candidates that host fraction alized excitations. However, detecting chiral character or proximity to these nontrivial states remains a challenge. Resonant Raman scattering can be a powerful tool for detecting chiral fluctuations, as the 𝐴 2⁢𝑔 channel probes excitations with broken time-reversal symmetry and local chiral order. Here, we use exact diagonalization to characterize the resonant 𝐴 2⁢𝑔 channel, alongside two-magnon scattering in 𝐵 1⁢𝑔 and 𝐸 𝑔 channels, for the Hubbard model on lattices with increasing levels of geometric spin frustration, where tuning the incident energy near the Mott gap reveals strong chiral spin excitation intensity. In conclusion, increased spin frustration in the Mott insulator results in an overall softening of the Raman 𝐴 2⁢𝑔 response, indicating a tendency toward low energy chiral-chiral fluctuations in Mott insulators with magnetic frustration and proximity to chiral spin liquid states that can potentially be tuned by external perturbations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND

Self‐Standing Chiral Covalent Organic Framework Thin Films with Full‐Color Tunable Guest‐Induced Circularly Polarized Luminescence

Abstract Exploring self‐standing chiral covalent organic framework (COF) thin films with controllable circularly polarized luminescence (CPL) is of paramount significance but remains a challenging task. Herein, we demonstrate the first example of self‐standing chiral COF films employing a polymerization‐dispersion‐filtration strategy. Pristine, low‐quality chiral COF films were produced by interfacial polymerization and then re‐dispersed into COF colloidal solutions. Via vacuum assisted assembly, these COF colloids were densely stacked and assembled into self‐standing, pure chiral COF films ( L‐ / D‐ CCOF‐F) that were transparent, smooth, crack‐free and highly crystalline. These films were tunable in thicknesses, areas, and roughness, along with strong diffuse reflectance circular dichroism (DRCD) and cyan CPL signals, showing an intrinsic luminescence asymmetric factor ( g lum ) of ~4.3×10 −3 . Furthermore, these COF films served as host adsorbents to load various achiral organic dye guests through adsorption. The effective chiral transfer and energy transfer between CCOF‐F and achiral fluorescent dyes endowed the dyes with strong chirality and tunable DRCD, resulting in intense, full‐color‐tunable solid‐state CPL. Notably, the ordered arrangement of dye guest molecules within the preferentially oriented chiral pores of CCOF‐F contributed to an amplified | g lum | factor of up to 7.2×10 −2 , which is state‐of‐the‐art for COF‐based CPL materials. This work provides new insights into the design and fabrication of self‐standing chiral COF films, demonstrating their great potential for chiroptical applications.

Tang, Xihao

Symmetry-engineered chiral magnetotransport in the correlated oxide SrNbO 3

Chiral transport in topological materials, arising from the interplay between topology and chirality, holds significant potential for energy-efficient spintronics and quantum information technologies through dissipationless, coherent charge flow. However, the emergence of chiral transport by tuning the electronic states of novel chiral materials is largely unexplored. Here, we report chiral transport driven by correlated Dirac fermions in SrNbO 3 epitaxial thin films, where strain-induced nonsymmorphic symmetry of oxygen octahedra tunes the material from metallic to Dirac states. Such symmetry-driven Dirac fermions feature a remarkable enhancement of electron mobility and magnetoresistance. Signatures of chiral transport induced by the chiral anomaly, including negative longitudinal magnetoresistance and twofold planar Hall oscillation, are observed in the Dirac semimetallic state, whereas they are absent in the metallic state of SrNbO 3 thin films. This work highlights a crucial role of symmetry engineering in generating chiral charge transport in oxide Dirac semimetals, opening an avenue to novel oxide-based topological and quantum devices.

Materials science

Confinement-induced chirality in phase-separated achiral polymer solutions

Self-organization of polymers in constrained geometries largely determines their applications in high-strength materials, photonics, and electronics. Chiral organization under confinement is well established for polymers with intrinsic molecular chirality; however, it has not been observed for achiral polymers. Here, we report the emergence of chirality in spatially confined solutions of achiral rigid-rod polymers. We show that kinetically arrested phase separation of polymer solutions confined to narrow capillaries resulted in alternating segments of isotropic and chiral nematic phases. The chiral structure of the nematic segments originated from the interplay between the constrained geometry, surface anchoring, orientational wetting, and elastic anisotropy of rigid-rod polymers. The catenoidal shape of the chiral structure recapitulated the morphology of biological chiral structures. These findings provide insight into the organization of soft matter under spatial confinement and offer a straightforward way to form chiral structures from achiral synthetic polymers.

Science & Technology - Other Topics

Engineered chirality of one-dimensional nanowires

The origin and function of chirality in DNA, proteins, and other building blocks of life represent a central question in biology. Observations of spin polarization and magnetization associated with electron transport through chiral molecules, known collectively as the chiral induced spin selectivity effect, suggest that chirality improves electron transfer. Using reconfigurable nanoscale control over conductivity at the LaAlO 3 /SrTiO 3 interface, we create chiral electron potentials that explicitly lack mirror symmetry. Quantum transport measurements on these chiral nanowires reveal enhanced electron pairing persisting to high magnetic fields (up to 18 tesla) and oscillatory transmission resonances as functions of both magnetic field and chemical potential. We interpret these resonances as arising from an engineered axial spin-orbit interaction within the chiral region. The ability to create one-dimensional electron waveguides with this specificity creates opportunities to test, via analog quantum simulation, theories about chirality and spin-polarized electron transport in one-dimensional geometries.

Science & Technology - Other Topics

Remote chirality transfer in low-dimensional hybrid metal halide semiconductors

In hybrid metal halide perovskites, chiroptical properties typically arise from structural symmetry breaking by incorporating a chiral A-site organic cation within the structure, which may limit the compositional space. Here we demonstrate highly efficient remote chirality transfer where chirality is imposed on an otherwise achiral hybrid metal halide semiconductor by a proximal chiral molecule that is not interspersed as part of the structure yet leads to large circular dichroism dissymmetry factors (g CD ) of up to 10-2. Density functional theory calculations reveal that the transfer of stereochemical information from the chiral proximal molecule to the inorganic framework is mediated by selective interaction with divalent metal cations. Anchoring of the chiral molecule induces a centro-asymmetric distortion, which is discernible up to four inorganic layers into the metal halide lattice. Additionally, this concept is broadly applicable to low-dimensional hybrid metal halides with various dimensionalities (1D and 2D) allowing independent control of the composition and degree of chirality.

14 SOLAR ENERGY

Chiral population analysis: a real space visualization of X-ray circular dichroism

The microscopic understanding of probing and controlling molecular chirality is of considerable interest. Numerous spectroscopic techniques are capable of monitoring molecular asymmetry and its consequences, ranging from the infrared to the X-ray regime. Resonant X-rays have long been used to investigate local atomic sites within molecules thanks to the localized nature of core electronic transitions. These techniques can be used to determine the extent to which chirality is a local versus a delocalized property. However, how to systematically partition dichroic contributions from the point of view of electronic structure simulations remains an open question. Here, we introduce the concept of chiral population analysis that connects chirality to the atomic orbital picture. In analogy with Mulliken population analysis, which assigns charges to atomic orbitals, chiral populations allow the dichroic response to be distributed among the participating atomic orbitals. This decomposition can be further visualized in real space by representing it in terms of isosurface plots, providing an intuitive way to connect the dichroic response to its origins. Thus chiral population analysis can be particularly useful to assess the extent to which a given electronic transition is sensitive to chirality as a local or global feature of the molecular geometry.

36 MATERIALS SCIENCE

Chiral effects and Joule heating in hot and dense matter

Initial states of dense matter with nonzero electron chiral imbalance could potentially give rise to strong magnetic fields through chiral plasma instability. Previous work indicated that unless chiral chemical potential is as large as the electron vector chemical potential, the growth of magnetic fields due to the instability is washed out by chirality flipping rate enabled by electron mass. We reexamine this claim in a broader range of parameters and find that at higher temperatures the hierarchy is reversed supporting a growing magnetic field for an initial electron chiral chemical potential much smaller than the electron vector chemical potential. Further, we identify a qualitatively new effect relevant for magnetized hot and dense medium where chiral magnetic effect (CME) sourced by density fluctuation acts as a powerful source of Joule heating. Remarkably, even modest chiral chemical potentials (keV) in such environment can deposit energy densities set by the QCD scale in a relatively short time of the order of a few milliseconds or seconds. We speculate how this mechanism makes CME-driven Joule heating a potentially critical ingredient in the dynamics of turbulent density fluctuation of supernovae and neutron star mergers.

Particle astrophysics

Influence of Alkyne Precursor Structure on Carbon Nanotube Chiral Distribution: Data-Dense Analysis Across Multiple Catalyst Types

Carbon nanotubes (CNTs) are a desirable material in the field of optoelectronics and semiconductors due to electronic properties (e.g., bandgap) that are dependent upon their chirality, defined by their diameter and lattice angle. Unfortunately, industrial-scale syntheses have yet to realize growth of a single desired chirality and instead rely on postsynthetic separation techniques to refine a chiral mixture, which increases process complexity and cost. Here, we studied the influence of precursor structure on chiral distribution, using a series of terminal alkyne precursors (acetylene, methylacetylene, vinylacetylene, 1-butyne, two enantiomers of 3-butyn-2-ol and a racemic mixture thereof) to grow CNTs across five transition-metal catalysts (Fe, FeMo, and three proportions of CoMo). Multiwavelength Raman spectroscopy on 5,145 spots (5 catalysts, 7 precursors, 3 lasers, and 49 distinct substrate locations on each) determined that acetylene grew the smallest diameter CNTs, while vinylacetylene produced fewer subnanometer CNTs. Though precursor structure did not dictate a uniform chiral shift, it was shown to broaden or narrow chiral distribution, while catalyst structure played a dominant role. In conclusion, this is consistent with metal-precursor binding occurring through unsaturated bonds in the hydrocarbons via the alkyne polymerization mechanism.

Carbon nanotubes

Interplay between Chiro-Optical and Spin Transport Properties in Chiral CdSe Quantum Dots

The chiral-induced spin selectivity (CISS) effect offers compelling approaches for manipulating spin-dependent processes in both chemistry and physics, yet the physical mechanism(s) underpinning CISS are still debated. Here we present a study of structure-property relationships in chiral quantum dot assemblies to identify attributes of CISS-based phenomena. Our results show that the circular dichroism (CD) strength of chiral CdSe quantum dots’ primary exciton transition correlates with two CISS properties, the propensity to transmit pure spin currents and to produce spin-polarized charge currents. While the spin-polarized charge current reverses its sign with a change in the polarity of the CD signal, the pure spin current transport does not. The trends in both transport types can be rationalized in terms of chirality-induced splitting of spin sub-bands, which are modulated by chiral symmetry breaking under charge transport through the CdSe quantum dots.

cadmium selenide