Search NASA⌕ Search

SEARCH · Search NASA

Results for “Circular dichroism”

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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Direct observation of the magnetic anisotropy of an Fe(II) spin crossover molecular thin film

Abstract In this work, we provide clear evidence of magnetic anisotropy in the local orbital moment of a molecular thin film based on the SCO complex [Fe(H 2 B(pz) 2 ) 2 (bipy)] (pz = pyrazol−1−yl, bipy = 2,2′−bipyridine). Field dependent x-ray magnetic circular dichroism measurements indicate that the magnetic easy axis for the orbital moment is along the surface normal direction. Along with the presence of a critical field, our observation points to the existence of an anisotropic energy barrier in the high-spin state. The estimated nonzero coupling constant of ∼2.47 × 10 −5 eV molecule −1 indicates that the observed magnetocrystalline anisotropy is mostly due to spin–orbit coupling. The spin- and orbital-component anisotropies are determined to be 30.9 and 5.04 meV molecule −1 , respectively. Furthermore, the estimated g factor in the range of 2.2–2.45 is consistent with the expected values. This work has paved the way for an understanding of the spin-state-switching mechanism in the presence of magnetic perturbations.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

The hTERT core promoter forms three parallel G-quadruplexes

The structure of the 68 nt sequence with G-quadruplex forming potential within the hTERT promoter is disputed. One model features a structure with three stacked parallel G-quadruplex units, while another features an unusual duplex hairpin structure adjoined to two stacked parallel and antiparallel quadruplexes. We report here the results of an integrated structural biology study designed to distinguish between these possibilities. As part of our study, we designed a sequence with an optimized hairpin structure and show that its biophysical and biochemical properties are inconsistent with the structure formed by the hTERT wild-type sequence. By using circular dichroism, thermal denaturation, nuclear magnetic resonance spectroscopy, analytical ultracentrifugation, small-angle X-ray scattering, molecular dynamics simulations and a DNase I cleavage assay we found that the wild type hTERT core promoter folds into a stacked, three-parallel G-quadruplex structure. The hairpin structure is inconsistent with all of our experimental data obtained with the wild-type sequence. All-atom models for both structures were constructed using molecular dynamics simulations. These models accurately predicted the experimental hydrodynamic properties measured for each structure. We found with certainty that the wild-type hTERT promoter sequence does not form a hairpin structure in solution, but rather folds into a compact stacked three-G-quadruplex conformation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

The solution structures of higher-order human telomere G-quadruplex multimers

Human telomeres contain the repeat DNA sequence 5'-d(TTAGGG), with duplex regions that are several kilobases long terminating in a 3' single-stranded overhang. The structure of the single-stranded overhang is not known with certainty, with disparate models proposed in the literature. We report here the results of an integrated structural biology approach that combines small-angle X-ray scattering, circular dichroism (CD), analytical ultracentrifugation, size-exclusion column chromatography and molecular dynamics simulations that provide the most detailed characterization to date of the structure of the telomeric overhang. We find that the single-stranded sequences 5'-d(TTAGGG)n, with n = 8, 12 and 16, fold into multimeric structures containing the maximal number (2, 3 and 4, respectively) of contiguous G4 units with no long gaps between units. The G4 units are a mixture of hybrid-1 and hybrid-2 conformers. In the multimeric structures, G4 units interact, at least transiently, at the interfaces between units to produce distinctive CD signatures. Global fitting of our hydrodynamic and scattering data to a worm-like chain (WLC) model indicates that these multimeric G4 structures are semi-flexible, with a persistence length of ~34 Å. Investigations of its flexibility using MD simulations reveal stacking, unstacking, and coiling movements, which yield unique sites for drug targeting.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Structure of native four-repeat satellite III sequence with non-canonical base interactions

Abstract Tandem-repetitive DNA (where two or more DNA bases are repeated numerous times) can adopt non-canonical secondary structures. Many of these structures are implicated in important biological processes. Human Satellite III (HSat3) is enriched for tandem repeats of the sequence ATGGA and is located in pericentromeric heterochromatin in many human chromosomes. Here, we investigate the secondary structure of the four-repeat HSat3 sequence 5′-ATGGA ATGGA ATGGA ATGGA-3′ using X-ray crystallography, NMR, and biophysical methods. Circular dichroism spectroscopy, thermal stability, native PAGE, and analytical ultracentrifugation indicate that this sequence folds into a monomolecular hairpin with non-canonical base pairing and B-DNA characteristics at concentrations below 0.9 mM. NMR studies at 0.05–0.5 mM indicate that the hairpin is likely folded-over into a compact structure with high dynamics. Crystallographic studies at 2.5 mM reveal an antiparallel self-complementary duplex with the same base pairing as in the hairpin, extended into an infinite polymer. The non-canonical base pairing includes a G–G intercalation sandwiched by sheared A–G base pairs, leading to a cross-strand four guanine stack, so called guanine zipper. The guanine zippers are spaced throughout the structure by A–T/T–A base pairs. Our findings lend further insight into recurring structural motifs associated with the HSat3 and their potential biological functions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Structure analysis of the telomere resolvase from the Lyme disease spirochete Borrelia garinii reveals functional divergence of its C-terminal domain

Borrelia spirochetes are the causative agents of Lyme disease and relapsing fever, two of the most common tick-borne illnesses. A characteristic feature of these spirochetes is their highly segmented genomes which consists of a linear chromosome and a mixture of up to approximately 24 linear and circular extrachromosomal plasmids. The complexity of this genomic arrangement requires multiple strategies for efficient replication and partitioning during cell division, including the generation of hairpin ends found on linear replicons mediated by the essential enzyme ResT, a telomere resolvase. Using an integrative structural biology approach employing advanced modelling, circular dichroism, X-ray crystallography and small-angle X-ray scattering, we have generated high resolution structural data on ResT from B. garinii. Our data provides the first high-resolution structures of ResT from Borrelia spirochetes and revealed active site positioning in the catalytic domain. We also demonstrate that the C-terminal domain of ResT is required for both transesterification steps of telomere resolution, and is a requirement for DNA binding, distinguishing ResT from other telomere resolvases from phage and bacteria. These results advance our understanding of the molecular function of this essential enzyme involved in genome maintenance in Borrelia pathogens.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Transient local secondary structure in the intrinsically disordered C‐term of the Albino3 insertase

Albino3 (Alb3) is an integral membrane protein fundamental to the targeting and insertion of light‐harvesting complex (LHC) proteins into the thylakoid membrane. Alb3 contains a stroma‐exposed C‐terminus (Alb3‐Cterm) that is responsible for binding the LHC‐loaded transit complex before LHC membrane insertion. Alb3‐Cterm has been reported to be intrinsically disordered, but precise mechanistic details underlying how it recognizes and binds to the transit complex are lacking, and the functional roles of its four different motifs have been debated. Using a novel combination of experimental and computational techniques such as single‐molecule fluorescence resonance energy transfer, circular dichroism with deconvolution analysis, site‐directed mutagenesis, trypsin digestion assays, and all‐atom molecular dynamics simulations in conjunction with enhanced sampling techniques, we show that Alb3‐Cterm contains transient secondary structure in motifs I and II. The excellent agreement between the experimental and computational data provides a quantitatively consistent picture and allows us to identify a heterogeneous structural ensemble that highlights the local and transient nature of the secondary structure. This structural ensemble was used to predict both the inter‐residue distance distributions of single molecules and the apparent unfolding free energy of the transient secondary structure, which were both in excellent agreement with those determined experimentally. We hypothesize that this transient local secondary structure may play an important role in the recognition of Alb3‐Cterm for the LHC‐loaded transit complex, and these results should provide a framework to better understand protein targeting by the Alb3‐Oxa1‐YidC family of insertases.

Okoto, Patience S.↗
DOE OSTI2025

Spin-Forbidden Excitations in the Magneto-optical Spectra of CrI 3 Tuned by Covalency

Spin-forbidden (Δ⁢𝑆 ≠0) multiplet excitations and their coupling to magnetic properties are of increasing importance for magneto-optical studies of correlated materials. Nonetheless, the mechanisms for optically brightening these transitions and their generality remain poorly understood. Here, we report magnetic circular dichroism (MCD) spectroscopy on the van der Waals ferromagnet (FM) CrI 3 . Previously unreported spin-forbidden (Δ⁢𝑆 =1) 4 𝐴 2⁢g → 2 𝐸 g / 2 𝑇 1⁢g Cr 3+ 𝑑⁢𝑑 excitations are observed near the ligand-to-metal charge-transfer excitation threshold. The assignment of these excitations and their Cr 3+ multiplet character is established through complementary Cr 𝐿 3 -edge resonant inelastic x-ray scattering measurements along with charge-transfer multiplet calculations and chemical trends in the chromium trihalide series (Cr⁢𝑋 3 , 𝑋 = Cl, Br, I). We utilize the high sensitivity of MCD spectroscopy to study the thickness-dependent optical response. The spin-forbidden excitations remain robust down to the monolayer limit, and we observe a significant magnetic-field dependence of the MCD spectrum across the antiferromagnetic-to-FM transition in few-layer samples. We preliminarily attribute this behavior to changes in the metal-ligand covalency with magnetic state. Our results clarify the magneto-optical response of CrI 3 and identify covalency as a central mechanism for the brightening and field tunability of spin-forbidden multiplet excitations.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Interfacial alloying contributions to the magnetic proximity effect in Pt/dysprosium iron garnet

The magnetic proximity effect (MPE), a magnetic response from a heavy metal layer induced by an adjacent magnetic layer, plays an important role in the behavior of heavy-metal/ferro- or ferrimagnet thin film heterostructures. However, in the case of heavy-metal/rare earth iron garnet bilayers the presence and magnitude of the MPE has been debated. We previously reported an MPE in a Pt/dysprosium iron garnet (DyIG) heterostructure where the two layers were grown without breaking vacuum, finding that the magnetic moment present in the Pt layer scales with the magnitude of the DyIG moment and varies nonmonotonically through the DyIG compensation temperature. However, the origin of the magnetic signal from the Pt layer was not identified. In contrast, Pt/DyIG grown with a vacuum break did not exhibit an MPE. Here we investigate the origin of the magnetic moment in the Pt layer using x-ray absorption spectroscopy, x-ray circular dichroism, composition mapping and simulations of ion bombardment. In conclusion, the results are consistent with the presence of an intermixed Fe-Dy-Pt interfacial alloy layer formed during the growth of the Pt on the DyIG and resulting in a measurable MPE.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Ferroaxial phonons in chiral and polar Ni⁢Co 2 ⁢Te⁢O 6

Perfect circular dichroism has been observed in Raman scattering by optical phonons in single chiral domain NiCo 2 TeO 6 crystals. The selection rules for optical phonons are determined by the combination of the chiral structure C and electric polarization P along the c axis. These two symmetry operations are equivalent to the ferroaxial order (C·P) = A, so the observed optical phonons are referred to as ferroaxial. For a given Raman scattering geometry, the observed effect may also be described as a perfect nonreciprocal propagation of the ferroaxial optical phonons, whose preferable q-vector direction is determined by the sign of A. Here, the combination of Raman scattering and polarization plane rotation of the transmitted white light allows for identification of the direction of electric polarization P in monodomain chiral crystals. In addition to the ferroaxial selection rules for optical phonons, a weaker ferroaxial dichroism was observed for the magnon peak at 18 cm −1 .

Altermagnets↗
DOE OSTI2024

Engineering exchange bias at the interface of self-polarized ultrathin ferroelectric Ba⁢Ti⁢O 3 and ferromagnetic La 0.67⁢ Sr 0.33 ⁢Mn⁢O 3

We investigate the emergence and optimization of conventional exchange bias (EB) in ultrathin (<10 nm) ferroelectric (FE) Ba⁢Ti⁢O 3 (BTO)/ferromagnetic (FM) La 0.67 ⁢Sr 0.33⁢ Mn⁢O 3 (LSMO) epitaxial bilayers without an antiferromagnetic (AFM) material. The EB originates from the electronic orbital reconstruction at the FE-FM interface due to the ferroelectric polarization. We achieve maximum EB of approximately 42 Oe with single-domain polarization in nine-unit-cell-thick BTO, setting the BTO thickness above the critical threshold for ferroelectricity yet below the thickness of strain relaxation and multidomain breakdown. Furthermore, the LSMO layer needs to be thick enough to sustain both the FM layer and polarization-induced AFM spin configuration at the LSMO/BTO interface, yet as thin as possible to enable the EB loop shift. The temperature, training, field, and thickness dependence of the EB confirm that the LSMO/BTO interface exhibits conventional EB despite its unconventional origin. Using x-ray magnetic circular dichroism, scanning transmission electron microscopy, and density-functional-theory calculations, we confirm that the macroscopic EB effect originates from the interfacial AFM spin configuration in LSMO driven by FE-induced d-orbital modifications in interfacial Mn ions. Thus, we engineer strong interfacial EB coupling in artificial multiferroics without a conventional AFM material by controlling FE polarization, highlighting the potential for advanced spintronic applications.

exchange bias↗
DOE OSTI2020

Magnetism of Ir 5 + -based double perovskites: Unraveling its nature and the influence of structure

A combination of x-ray-diffraction, x-ray absorption, x-ray magnetic circular dichroism, macroscopic magnetization, and muon-spin relaxation measurements is used to investigate the interplay between structure (both crystallography and microstructure) and magnetism in Sr 2 YIrO 6 as a function of both chemical (Ca-doping) and physical (hydrostatic) pressure. X-ray absorption spectroscopy clearly shows that the physical pressure is more effective in modifying the structure. On the other hand, the dichroic measurements evidence a constant magnetic signal with physical pressure and strong differences with Ca-doping. Muon-spin relaxation reveals the presence of magnetic order, even when this is hidden in the magnetization data. From the combined analysis, the magnetic results are explained in terms of the presence of Ir 6+ or Ir 4+ ions in magnetic clusters, most likely located at and triggered by antisite disorder. The measurements under high physical pressure indicate that the magnetic state is independent of the crystallographic details such as Ir-O distances and Ir-O-Y angles.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Spontaneous Hall effect enhanced by local Ir moments in epitaxial Pr 2 Ir 2 O 7 thin films

Rare-earth pyrochlore iridates ( RE 2 Ir 2 O 7 ) consist of two interpenetrating cation sublattices, the RE with highly frustrated magnetic moments, and the iridium with extended conduction orbitals significantly mixed by spin-orbit interactions. The coexistence and coupling of these two sublattices create a landscape for discovery and manipulation of quantum phenomena such as the topological Hall effect, massless conduction bands, and quantum criticality. Thin films allow extended control of the material system via symmetry-lowering effects such as strain. While bulk Pr 2 Ir 2 O 7 shows a spontaneous hysteretic Hall effect below 1.5 K, we observe the effect at elevated temperatures up to 15 K in epitaxial thin films on (111) yttria-stabilized zirconia (YSZ) substrates synthesized via solid-phase epitaxy. Similar to the bulk, the lack of observable long-range magnetic order in the thin films points to a topological origin. We use synchrotron-based element-specific x-ray diffraction and x-ray magnetic circular dichroism to compare powders and thin films to attribute the spontaneous Hall effect in the films to localization of the Ir moments. Further, we link the thin-film Ir local moments to lattice distortions absent in the bulklike powders. We conclude that the elevated-temperature spontaneous Hall effect is caused by the topological effect originating either from the Ir or Pr sublattice, with interaction strength enhanced by the Ir local moments. This spontaneous Hall effect with weak net moment highlights the effect of vanishingly small lattice distortions as a means to discover topological phenomena in metallic frustrated magnetic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Antiferromagnetic domain switching modulated by an ultrathin Co interlayer in the Fe/Co/CoO/MgO(001) system

Using a combination of hysteresis loop, Kerr microscope, and x-ray magnetic circular dichroism measurements, in this study we investigated the antiferromagnetic (AFM) domain switching process modulated by the sub-nm thick Co inserting layer in a single crystalline Fe/Co/CoO/MgO(001). The CoO AFM domain switching occurs at lower temperature for the thicker Co interlayer, and the activation energy barrier of CoO AFM domain switching decreases as the Co interlayer thickness increases. The exchange coupling strength between the AFM spins in CoO layer and the ferromagnetic spins in the Fe/Co bilayer is found to be independent of the Co layer thickness. Our results suggest an approach to modulate the dynamic properties of AFM domains with an interfacial modification.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Cation- and lattice-site-selective magnetic depth profiles of ultrathin Fe 3 O 4 (001) films

A detailed understanding of ultrathin film surface properties is crucial for the proper interpretation of spectroscopic, catalytic, and spin-transport data. We present x-ray magnetic circular dichroism (XMCD) and x-ray resonant magnetic reflectivity (XRMR) measurements on ultrathin Fe 3 O 4 films to obtain magnetic depth profiles for the three resonant energies corresponding to the different cation species F e o c t 2 + , F e t e t 3 + , and F e o c t 3 + located on octahedral and tetrahedral sites of the inverse spinel structure of Fe 3 O 4 . By analyzing the XMCD spectrum of Fe 3 O 4 using multiplet calculations, the resonance energy of each cation species can be isolated. Performing XRMR on these three resonant energies yields magnetic depth profiles that each correspond to one specific cation species. The depth profiles of both kinds of Fe 3+ cations reveal a (3.9 ± 1.0) -Å -thick surface layer of enhanced magnetization, which is likely due to an excess of these ions at the expense of the F e o c t 2 + species in the surface region. The magnetically enhanced F e t e t 3 + layer is additionally shifted about 2.9 ± 0.4 Å farther from the surface than the F e o c t 3 + layer.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Magnetocapacitance effect and magnetoelectric coupling in type-II multiferroic HoFeWO 6

We have investigated the multiferroicity and magnetoelectric (ME) coupling in HoFeWO 6 . With a noncentrosymmetric polar structure (space group Pna2 1 ) at room temperature, this compound shows an onset of electric polarization with an antiferromagnetic ordering at the Néel temperature (T N ) of 17.8 K. The magnetic properties of the polycrystalline samples were studied by DC and AC magnetization and heat capacity measurements. The metamagnetic behavior at low temperatures was found to be directly related to the dielectric properties of the compound. In particular, field-dependent measurements of capacitance show a magnetocapacitance (MC) effect with double-hysteresis loop behavior in direct correspondence with the magnetization. Our x-ray diffraction results show the Pna2 1 structure down to 8 K and suggest the absence of a structural phase transition across T N . Soft x-ray absorption spectroscopy and soft x-ray magnetic circular dichroism (XMCD) measurements at the Fe L 2,3 and Ho M 4,5 edges revealed the oxidation state of Fe and Ho cations to be 3+. Fe L 2,3 XMCD further shows that Fe 3+ cations are antiferromagnetically ordered in a noncollinear fashion with spins arranged 90° with respect to each other. Our findings show that HoFeWO 6 is a type-II multiferroic exhibiting a MC effect. Furthermore, the observed MC effect and the change in polarization by the magnetic field, as well as their direct correspondence with magnetization, further support the strong ME coupling in this compound.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Eshelby-twisted three-dimensional moiré superlattices

Twisted bilayers of van der Waals materials have recently attracted great attention due to their tunable, strongly correlated phenomena. In this work, we investigate the chirality-specific physics in three-dimensional moiré superlattices induced by Eshelby twist. Our direct density functional theory calculations reveal helical rotation leads to optical circular dichroism and chirality-specific nonlinear Hall effect, even though there is no magnetization or magnetic field. Both these phenomena can be reversed by changing the structural chirality. This provides a path to constructing chirality-specific materials.

2-dimensional systems↗
DOE OSTI2021

Strongly anisotropic antiferromagnetic coupling in EuFe 2 As 2 revealed by stress detwinning

Of all parent compounds of iron-based high-temperature superconductors, EuFe 2 As 2 exhibits by far the largest magnetostructural coupling due to the sizable biquadratic interaction between Eu and Fe moments. While the coupling between Eu antiferromagnetic order and Fe structural/antiferromagnetic domains enables rapid field detwinning, this prevents simple magnetometry measurements from extracting the critical fields of the Eu metamagnetic transitions. Furthermore we measure these critical fields by combining x-ray magnetic circular dichroism spectroscopy with in-situ tunable uniaxial stress and applied magnetic field. The combination of two tuning knobs allows us to separate the stressdetwinning of structural domains from the field-induced reorientation of Eu moments. Intriguingly, from the critical field values we find that the Eu interplanar interaction is strongly anisotropic. We argue that this anisotropic exchange term is likely a consequence of the strong anisotropy in the magnetically ordered Fe layer, which highlights the non-trivial interplay between Eu-Fe magnetism in this system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Origins of electronic bands in the antiferromagnetic topological insulator MnBi 2 Te 4

Despite the rapid progress in understanding the first intrinsic magnetic topological insulator MnBi 2 Te 4 , its electronic structure remains a topic under debates. In this work, we perform a thorough spectroscopic investigation into the electronic structure of MnBi 2 Te 4 via laser-based angle-resolved photoemission spectroscopy. Through quantitative analysis, we estimate an upper bound of 3 meV for the gap size of the topological surface state. Furthermore, our circular dichroism measurements reveal band chiralities for both the topological surface state and quasi-2D bands, which can be well reproduced in a band hybridization model. A numerical simulation of energy-momentum dispersions based on a four-band model with an additional step potential near the surface provides a promising explanation for the origin of the quasi-2D bands. Our study represents a solid step forward in reconciling the existing controversies in the electronic structure of MnBi 2 Te 4 , and provides an important framework to understand the electronic structures of other relevant topological materials MnBi 2n Te 3n+1 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗