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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.

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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Strong Ferromagnetic Exchange Coupling and Single-Molecule Magnetism in MoS 4 3– -Bridged Dilanthanide Complexes

We report the synthesis and characterization of the trinuclear 4d-4f compounds [Co(C 5 Me 5 ) 2 ][(C 5 Me 5 ) 2 Ln(μ-S) 2 Mo(μ-S) 2 Ln(C 5 Me 5 ) 2 ], 1-Ln (Ln = Y, Gd, Tb, Dy), containing the highly polarizable MoS 4 3 - bridging unit. UV-Vis-NIR diffuse reflectance spectra and DFT calculations of 1-Ln reveal a low-energy metal-to-metal charge transfer transition assigned to charge transfer from the singly occupied 4d z 2 orbital of Mo V to the empty 5d orbitals of the lanthanides (4d in the case of 1-Y ), mediated by sulfur-based 3p orbitals. Electron paramagnetic resonance spectra collected for 1-Y in a tetrahydrofuran solution show large 89 Y hyperfine coupling constants of A ⊥ = 23 MHz and A || = 26 MHz, indicating the presence of significant yttrium-localized unpaired electron density. Magnetic susceptibility data support similar electron delocalization and ferromagnetic Ln-Mo exchange for 1-Gd , 1-Tb , and 1-Dy . This ferromagnetic exchange gives rise to an S = 15/2 ground state for 1-Gd and one of the largest magnetic exchange constants involving Gd III observed to date, with J Gd-Mo = +16.1(2) cm -1 . Additional characterization of 1-Tb and 1-Dy by ac magnetic susceptibility measurements reveals that both compounds exhibit slow magnetic relaxation. Although a Raman magnetic relaxation process is dominant for both 1-Tb and 1-Dy , an extracted thermal relaxation barrier of U eff = 68 cm -1 for 1-Dy is the largest yet reported for a complex containing a paramagnetic 4d metal center. Furthermore, these results provide a potentially generalizable route to enhanced n d-4f magnetic exchange, revealing opportunities for the design of new n d-4f single-molecule magnets and bulk magnetic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

As–Se Pentagonal Linkers to Induce Chirality and Polarity in Mixed-Valent Fe–Se Tetrahedral Chains Resulting in Hidden Magnetic Ordering

A novel mixed-valent hybrid chiral and polar compound, Fe 7 As 3 Se 12 (en) 6 (H 2 O), has been synthesized by a single-step solvothermal method. The crystal structure consists of 1D [Fe 5 Se 9 ] chains connected via [As 3 Se 2 ]–Se pentagonal linkers and charge-balancing interstitial [Fe(en) 3 ] 2+ complexes (en = ethylenediamine). Neutron powder diffraction verified that interstitial water molecules participate in the crystal packing. Magnetic polarizability of the produced compound was confirmed by X-ray magnetic circular dichroism (XMCD) spectroscopy. X-ray absorption spectroscopy (XAS) and 57 Fe Mössbauer spectroscopy showed the presence of mixed-valent Fe 2+ /Fe 3+ in the Fe–Se chains. Magnetic susceptibility measurements reveal strong antiferromagnetic nearest neighbor interactions within the chains with no apparent magnetic ordering down to 2 K. Hidden short-range magnetic ordering below 70 K was found by 57 Fe Mössbauer spectroscopy, showing that a fraction of the Fe 3+ /Fe 2+ in the chains are magnetically ordered. Nevertheless, complete magnetic ordering is not achieved even at 6 K. Analysis of XAS spectra demonstrates that the fraction of Fe 3+ in the chain increases with decreasing temperature. Computational analysis points out several competing ferrimagnetic ordered models within a single chain. Here, this competition, together with variation in the Fe oxidation state and additional weak intrachain interactions, is hypothesized to prevent long-range magnetic ordering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Solvent Dynamics Are Critical to Understanding Carbon Dioxide Dissolution and Hydration in Water

Simulations of carbon dioxide (CO 2 ) in water may aid in understanding the impact of its accumulation in aquatic environments and help advance technologies for carbon capture and utilization (via, e.g., mineralization). Quantum mechanical (QM) simulations based on static molecular models with polarizable continuum solvation poorly reproduce the energetics of CO 2 hydration to form carbonic acid in water, independent of the level of QM theory employed. Only with density-functional-theory-based molecular dynamics and rare-event sampling, followed by energy corrections based on embedded correlated wavefunction theory (in conjunction with density functional embedding theory), can a close agreement between theory and experiment be achieved. Such multilevel simulations can serve as benchmarks for simpler, less costly models, giving insight into potential errors of the latter. The strong influence of sampling/averaging over dynamical solvent configurations on the energetics stems from the difference in polarity of both the transition state and product (both polar) versus the reactant (nonpolar). When a solute undergoes a change in polarity during reaction, affecting its interaction with the solvent, careful assessment of the energetic contribution of the solvent response to this change is critical. Here, we show that static models (without structural sampling) that incorporate three explicit water molecules can yield far superior results than models with more explicit water molecules because fewer water molecules yield less configurational artifacts. Static models intelligently incorporating both explicit (molecules directly participating in the reaction) and implicit solvation, along with a proper QM theory, e.g., CCSD(T) for closed-shell systems, can close the accuracy gap between static and dynamic models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Local Chemical Clustering Enabled Ultrahigh Capacitive Energy Storage in Pb-Free Relaxors

Designing Pb-free relaxors with both a high capacitive energy density (W rec ) and high storage efficiency (η) remains a remarkable challenge for cutting-edge pulsed power technologies. Local compositional heterogeneity is crucial for achieving complex polar structure in solid solution relaxors, but its role in optimizing energy storage properties is often overlooked. Here, in this paper, we report that an exceptionally high W rec of 15.2 J cm –3 along with an ultrahigh η of 91% can be achieved through designing local chemical clustering in Bi 0.5 Na 0.5 TiO 3 –BaTiO 3 -based relaxors. A three-dimensional atomistic model derived from neutron/X-ray total scattering combined with reverse Monte Carlo method reveals the presence of subnanometer scale clustering of Bi, Na, and Ba, which host differentiated polar displacements, and confirming the prediction by density functional theory calculations. This leads to a polar state with small polar clusters and strong length and direction fluctuations in unit-cell polar vectors, thus manifesting improved high-field polarizability, steadily reduced hysteresis, and high breakdown strength macroscopically. The favorable polar structure features also result in a unique field-increased η, excellent stability, and superior discharge capacity. Our work demonstrates that the hidden local chemical order exerts a significant impact on the polarization characteristic of relaxors, and can be exploited for accessing superior energy storage performance.

25 ENERGY STORAGE↗
DOE OSTI2023

Combining Force Fields and Neural Networks for an Accurate Representation of Chemically Diverse Molecular Interactions

A key goal of molecular modeling is the accurate reproduction of the true quantum mechanical potential energy of arbitrary molecular ensembles with a tractable classical approximation. The challenges are that analytical expressions found in general purpose force fields struggle to faithfully represent the intermolecular quantum potential energy surface at close distances and in strong interaction regimes; that the more accurate neural network approximations do not capture crucial physics concepts, e.g., nonadditive inductive contributions and application of electric fields; and that the ultra-accurate narrowly targeted models have difficulty generalizing to the entire chemical space. We therefore designed a hybrid wide-coverage intermolecular interaction model consisting of an analytically polarizable force field combined with a short-range neural network correction for the total intermolecular interaction energy. Here, we describe the methodology and apply the model to accurately determine the properties of water, the free energy of solvation of neutral and charged molecules, and the binding free energy of ligands to proteins. The correction is subtyped for distinct chemical species to match the underlying force field, to segment and reduce the amount of quantum training data, and to increase accuracy and computational speed. For the systems considered, the hybrid ab initio parametrized Hamiltonian reproduces the two-body dimer quantum mechanics (QM) energies to within 0.03 kcal/mol and the nonadditive many-molecule contributions to within 2%. Simulations of molecular systems using this interaction model run at speeds of several nanoseconds per day.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Metal–Organic Frameworks as a Tunable Platform to Deconvolute Stereoelectronic Effects on the Catalytic Activity of Thioanisole Oxidation

The local environment of a metal active site plays an important role in affecting catalytic activity and selectivity. In re-cent studies, tailoring the behavior of a molybdenum-based active site via modulation of the first coordination sphere has led to improved thioanisole oxidation performance, but disentangling electronic effects from steric influences that arise from these modifications is nontrivial, especially in heterogeneous systems. To this end, the tunability of metal–organic frameworks (MOFs) makes them promising scaffolds for controlling the coordination sphere of a heterogene-ous, catalytically-active metal site while offering additional, attractive features such as crystallinity and high porosity. Herein, we report a variety of MOF-supported Mo species, which were investigated for catalytic thioanisole oxidation to methyl phenyl sulfoxide and/or methyl phenyl sulfone using tert-butyl hydroperoxide (tBHP) as the oxidant. In particular, MOFs of contrasting node architectures were targeted, presenting a unique opportunity to investigate ste-reoelectronic control of Mo active sites in a systematic manner. A Zr 6 -based MOF, NU-1000, was employed along with its sulfated analog Zr 6 -based NU-1000-SO 4 to anchor a dioxymolybdenum species, which enabled examination of sup-port-mediated active site polarizability on catalytic performance. In addition, a MOF containing a mixed metal node, Mo-MFU-4l, was used to probe the stereoelectronic impact of an N-donor ligand environment on the catalytic activity of the transmetalated Mo center. Furthermore, characterization techniques including single crystal X-ray diffraction, were concomi-tantly used with reaction kinetic profiles to better comprehend the dynamics of different Mo active sites, thus correlat-ing structural change with activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Highly Conjugated Porphyrin Arrays Enable Optical Resolution of Ferromagnetic and Antiferromagnetic Aligned States of the Triplet Exciton and an Incorporated Stable Radical

Well-defined photogenerated molecular spin systems have potential utility in spintronics and quantum information science (QIS). Because molecular magnetic, optical, and electronic properties can be controlled by design, diverse spin systems can be prepared at modest temperatures. Photogenerated molecular spin systems often involve states prepared from the interaction of excitons and charges. Resolving the nature of electron spin alignment in photogenerated spin states described by the coupling of a triplet exciton and a stable radical commonly relies on EPR spectroscopy. Here, we describe ethyne-bridged (porphinato)metal ( PM n ) oligomers that incorporate a macrocycle-bound Cu(II) radical center. Upon photoexcitation of such PM n arrays, a singdoublet ( 2 S 1 ) state is formed; ultrafast internal conversion (IC) then produces a tripdoublet ( 2 T 1 ) state, which undergoes intersystem crossing (ISC) to produce a tripquartet ( 4 T 1 ) state, before relaxation to the ground state ( 2 S 0 ). These highly conjugated Cu(II) radical-containing PMn arrays enable direct observation of copper porphyrin 2 T 1 → 4 T 1 ISC dynamics from the biexponential decay of the near-infrared (NIR) 2,4 T 1 → 2,4 T n transient absorption manifold. Multireference n-electron valence perturbation theory (NEVPT2) computations illuminate how PM n electronic structure controls the relaxation dynamics of these long-lived (>10 ns) electronically excited multiplet states. These studies show that highly conjugated and polarizable porphyrin arrays incorporating stable spin centers provide rare π-delocalized systems where the ferromagnetic and antiferromagnetic alignment between a triplet exciton and a stable radical are both spectrally resolved and addressable using transient optical spectroscopy at wavelengths exceeding 1 μm, providing new opportunities to QIS.

14 SOLAR ENERGY↗
DOE OSTI2025

Crystalline Order Yet Glass-Like Heat Transport Driven by Hidden Local Distortions as the Structural Origin of Ultralow Thermal Conductivity in AgErTe 2

Given their rich chemical diversity and the interplay among the p-, d-, and f-orbitals of chalcogens, transition metals, and lanthanides, respectively, rare-earth transition-metal chalcogenides exhibit a wide variety of structural, magnetic, and transport phenomena. As a result, they form a particularly appealing platform for investigating structure–property relationships, emergent electronic and magnetic behaviors, and thermal transport. Here we investigate AgErTe 2 as a model system to understand phonon-glass behavior in ordered crystalline solids, which establishes the design principles for thermal barrier coatings and next-generation thermoelectrics. The local bonding asymmetry and lattice softness suppress the inherently low lattice thermal conductivity, resembling the characteristics of amorphous materials. This suppression is significantly influenced by local off-centering of Ag atoms, which breaks lattice periodicity while maintaining global crystallinity. The presence of antibonding states just below the Fermi level, arising from Ag 4d and Te 5p orbital interactions, leads to lattice softening and destabilizes ideal tetrahedral coordination, resulting in a pseudo Jahn–Teller distortion. Furthermore, the coexistence of weaker, more polarizable Ag–Te bonds and stronger Er–Te bonds creates a complex vibrational landscape enriched with low-frequency modes and enhanced phonon scattering. A pronounced disparity in interatomic force constants gives rise to highly localized, low-energy optical phonons linked to Ag rattling. These flat vibrational modes exhibit strong coupling with transverse acoustic phonons, resulting in ultrashort phonon lifetimes and mean free paths approaching interatomic distances. These features collectively enhance phonon scattering across a broad range of length and energy scales. This work offers a framework for engineering suppressed thermal conductivity in crystalline systems without the introduction of alloying elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Alkali-Metal Interlocking of 2D V 4 O 10 Sheets Defines Discretized Interlayer Shear Relationships

Low-dimensional materials manifest structural anisotropy, quantum confinement, and tightly bound excitonic states, which make them attractive building blocks that can be assembled within three-dimensional laterally stitched heterostructures, stacked van der Waals solids, and complex moiré superlattices. Ion intercalation in the galleries between layered materials provides a means of modifying interlayer separation and coupling, but it is also known to drive the shearing of the layers. In this article, we explore the distinct ligand coordination environments afforded by vanadyl oxygens of singular [V 4 O 10 ] sheets and examine how the size, polarizability, and stoichiometry of Group I cations sandwiched between such layers determine the interlocking of the sheets in stacked structures. Based on the topochemical insertion of alkali-metal ions into the layered λ-V 2 O 5 , we identify seven types of guest ion coordination sites discretized into four distinct regimes of interlayer shear in units of half octahedral widths. The coordination preferences of intercalated cations govern how they interlock 2D [V 4 O 10 ] sheets and engender specific shear conformations. We present evidence that static and dynamic disorder in guest ion arrangement modulate the magnetic structure of the intercalated compounds based on electrostatic polarization, localization of charge and spin density, and lattice distortion. The results illustrate the use of topochemical ion insertion to modulate stacking relationships and magnetic transition characteristics.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Assessing the Impacts of Conformational Fluxionality on Copper(II/I) Electron Transfer Self-Exchange

Typical Cu(II/I) complexes exhibit hallmark structural changes during their electron transfer (ET) reactions that result from the (pseudo) Jahn-Teller distortions and changes in polarizability inherent to their d 10 / d 9 configurations. Given that such structural changes incur large reorganization energy penalties, slow the rates of ET are characteristic of these compounds. Notwithstanding, we recently reported a set of Cu(II/I) complexes that undergo significant and well-defined structural changes during their redox reactions yet exhibit rapid (> 10 5 M ‒1 s ‒1 ) ET self-exchange rate constants ( k 11 ). To explain these results we proposed a pre-equilibrium model in which inherent conformational fluxionality in one of the two oxidation states provides access to pathways involving lower reorganization energies during the ET event. Herein we report our results testing this hypothesis through the preparation and study of a homologous series of compounds exhibiting varying extents of con-formational fluxionality in the Cu(I) state. We characterize these compounds electrochemically, structurally, and by varia-ble temperature NMR spectroscopy to provide experimental evidence for increase fluxionality across the series. We then correlate the trend with increasing k 11 through NMR linewidth broadening experiments, further taking care to define the impacts of solvent impurities therein. Finally, the nature of the conformational rearrangements, and their relation to increased k 11 are explored computationally to reveal differential Boltzmann populations of conformers across the series. The cumulative results of these studies support a previously underappreciated strategy for overcoming barriers to slow ET kinetics: via the incorporation of conformational fluxionality.

Singh, Aditi↗
DOE OSTI2025

A Universal Model of Cation Effects in Electrocatalysis

Electrolyte cations are conventionally viewed as inert spectators in electrocatalysis. However, a wealth of observations show that catalytic rates are often highly sensitive to cation identity. Despite their prevalence, these cation effects have resisted a unified mechanistic explanation, with different physical phenomena implicated across reaction chemistries, catalyst compositions, and choice of solvent. In this perspective, we describe a general framework for understanding cation effects in electrocatalysis based on electrostatics. We argue that cations influence reaction rates by modifying the strength of the electric field present at the catalyst surface, which alters the energetics of adsorbed intermediates and transition states according to their dipole moments and polarizabilities. The magnitude of this field depends on how cations arrange at the electrode surface, controlled by their size, shape, solvation, and packing efficiency. Cations that can arrange more densely result in a steeper potential drop at the electrode surface and consequently a stronger electric field. Our model further identifies two criteria for observing cation effects: (1) the operating potential must be negative of the electrode’s potential of zero total charge, ensuring that cations accumulate at the interface, and (2) the energetics of the kinetically relevant elementary step must be field sensitive. This framework reconciles previously inconsistent trends, including why cation effects appear only for some catalysts, why reaction selectivity is sensitive to cation identity, and why activity can increase with cation size on certain metals but decrease on others. Supported by kinetic measurements, spectroscopy, and atomistic simulations, the model provides both conceptual value for building intuition about catalysis at charged interfaces and predictive value for anticipating trends for new reactions, catalysts, and electrolytes. We conclude by highlighting the importance of electric fields across electrochemical, thermochemical, and biological catalysis and propose that considering the electrostatic environment around active sites offers new opportunities for improving activity and selectivity.

cation effects↗
DOE OSTI2024

Permeability and Induced Polarization of Mudstones

Electrical measurements can be used to estimate hydraulic properties such as permeability ( k ) in sedimentary rocks. Previous work has focused on sandstones, siltstones, and carbonates, while investigations on mudstones have rarely been reported. In this study, we report on electrical geophysical measurements for 23 mudstone samples using an experimental approach designed to reliably saturate these low permeability mudstones. The modified Hagen-Poiseuille model linking permeability to the formation factor ( F ) and an effective pore radius ( r ) provides an excellent fit to the data set with a near-constant pore radius, indicating that the effective porosity (1/ F ) is the controlling factor on k . In these samples, the surface area normalized to pore volume ( S por ), frequently used in permeability estimation models, varies by 1–2 orders of magnitude and is thus not a reliable proxy of the inverse effective hydraulic radius. The formation factor also exerts the primary control on induced polarization (IP) parameters, whereas Spor shows no relation to the IP parameters. A strong linear relationship is found between IP parameters (imaginary conductivity and normalized chargeability) and surface conductivity, although the proportionality factor is significantly lower than those observed in more permeable rocks and sediments. Apparent relationships between the polarization strength-derived and time constant-derived geophysical length scales and the effective hydraulic radius appear to be driven by variations in the electrochemical parameters (i.e., specific polarizability and diffusion coefficient). Overall, these findings emphasize that predicting hydraulic properties from electrical measurements in fine-grained rocks remains challenging and requires further investigation into the electrochemical properties involved.

58 GEOSCIENCES↗
DOE OSTI2021

Creation of an unexpected plane of enhanced covalency in cerium(III) and berkelium(III) terpyridyl complexes

Abstract Controlling the properties of heavy element complexes, such as those containing berkelium, is challenging because relativistic effects, spin-orbit and ligand-field splitting, and complex metal-ligand bonding, all dictate the final electronic states of the molecules. While the first two of these are currently beyond experimental control, covalent M‒L interactions could theoretically be boosted through the employment of chelators with large polarizabilities that substantially shift the electron density in the molecules. This theory is tested by ligating Bk III with 4’-(4-nitrophenyl)-2,2’:6’,2”-terpyridine (terpy*), a ligand with a large dipole. The resultant complex, Bk(terpy*)(NO 3 ) 3 (H 2 O)·THF, is benchmarked with its closest electrochemical analog, Ce(terpy*)(NO 3 ) 3 (H 2 O)·THF. Here, we show that enhanced Bk‒N interactions with terpy* are observed as predicted. Unexpectedly, induced polarization by terpy* also creates a plane in the molecules wherein the M‒L bonds trans to terpy* are shorter than anticipated. Moreover, these molecules are highly anisotropic and rhombic EPR spectra for the Ce III complex are reported.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

E(n)-Equivariant cartesian tensor message passing interatomic potential

Machine learning potential (MLP) has been a popular topic in recent years for its capability to replace expensive first-principles calculations in some large systems. Meanwhile, message passing networks have gained significant attention due to their remarkable accuracy, and a wave of message passing networks based on Cartesian coordinates has emerged. However, the information of the node in these models is usually limited to scalars, and vectors. In this work, we propose High-order Tensor message Passing interatomic Potential (HotPP), an E(n) equivariant message passing neural network that extends the node embedding and message to an arbitrary order tensor. By performing some basic equivariant operations, high order tensors can be coupled very simply and thus the model can make direct predictions of high-order tensors such as dipole moments and polarizabilities without any modifications. The tests in several datasets show that HotPP not only achieves high accuracy in predicting target properties, but also successfully performs tasks such as calculating phonon spectra, infrared spectra, and Raman spectra, demonstrating its potential as a tool for future research.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2025

Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides

The trivalent actinides are produced in the nuclear fuel cycle during power production and provide the largest long-term radiation dose in used nuclear fuel. It is ideal for these elements to be removed from used nuclear fuel for disposal and a necessity for fuel recycling. A key challenge to this is the similarity of chemical behavior of the trivalent actinides to the lanthanides that are also present as fission products in used fuel. Thus far, some of the most effective separations of actinides from lanthanides utilise chelating agents containing sulfur moieties such as dithiophosphinates that selectively bind to actinide ions because of a greater bond covalency relative to lanthanide ions. Typically, greater differences between actinide and lanthanide ions are observable the more ligands and chelators bonds have a covalent character. Here, a series of complexes of the trivalent actinides Np(III) through Cf(III) (excluding Bk(III)) with maleonitrile-1,2-dithiolate (mnt 2– ) are synthesized along with their lanthanide counterparts (La(III) – Nd(III), Sm(III) – Gd(III), Dy(III)), in order to characterize the nature of chemical bonds with these metal ions and a polarizable, non-innocent, sulfur-donor ligand. The metal-sulfur bonds in these complexes trend shorter than measured for lanthanides with equivalent ionic radii. However, particularly large deviations are observed in the neptunium and plutonium complexes in both structure and bonding, resulting in a nonlinear bond length trendline for the actinide series. Density Functional Theory (DFT) calculations with Quantum Theory of Atoms in Molecules (QTAIM) and Natural Bond Order (NBO) analyses indicate that for the neptunium and plutonium complexes, the presence of increased 5f-orbital participation, energy degeneracy of the metal and ligand orbitals, and the structure packing result in shortened M–S bonds. The stabilization of the energy of the 5f-orbitals and the decrease in f-contribution to bonding orbitals in the later actinides results in structural properties more similar to the lanthanide complexes.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2025

TiSe 2 is a band insulator created by lattice fluctuations, not an excitonic insulator

TiSe 2 is a narrow-gap insulator with a rich array of unique properties. In addition to being a superconductor under certain modifications, it is commonly thought to be a rare realisation of an excitonic insulator. Below 200 K, TiSe 2 undergoes a transition from a high-symmetry ($P\bar{3}m1$) phase to a low-symmetry ($P\bar{3}c1$) charge density wave (CDW). Here we establish that it is indeed an insulator in both $P\bar{3}m1$ and $P\bar{3}c1$ phases. However, the insulating state is driven not by excitonic effects but by symmetry-breaking. In the CDW phase it is static. At high temperature, thermally driven instantaneous deviations from $P\bar{3}m1$ break the symmetry on the characteristic time scale of a phonon. Even though the time-averaged lattice structure assumes $P\bar{3}m1$ symmetry, the time-averaged energy band structure is closer to the CDW phase - a rare instance of a metal-insulator transition induced by dynamical symmetry breaking. We establish these conclusions from quasiparticle self-consistent GW (QSGW) and many-body calculations (QS$G\widehat{W}$), in combination with molecular dynamics simulations to capture the effects of thermal disorder. The many-body theory includes explicitly ladder diagrams in the polarizability, which incorporates excitonic effects in an ab initio manner. We find that the excitonic modification to the potential is weak, ruling out the possibility that TiSe 2 is an excitonic insulator.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Spontaneous orbital polarization in the nematic phase of FeSe

The origin of nematicity in FeSe remains a critical outstanding question towards understanding unconventional superconductivity in proximity to nematic order. To understand what drives the nematicity, it is essential to determine which electronic degree of freedom admits a spontaneous order parameter independent from the structural distortion. In this work, we use X-ray linear dichroism at the Fe K pre-edge to measure the anisotropy of the 3d orbital occupation as a function of in situ applied stress and temperature across the nematic transition. Along with using X-ray diffraction to precisely quantify the strain state, we reveal a lattice-independent, spontaneously ordered orbital polarization within the nematic phase, as well as an orbital polarizability that diverges as the transition is approached from above. These results provide strong evidence that spontaneous orbital polarization serves as the primary order parameter of the nematic phase.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Magnetic brightening and nanoscale imaging of spin-polarized helical edge modes in ZrTe 5

Efficient charge transport remains a fundamental challenge for nanoelectronic devices, as their performance is constrained by high dissipation and the impedance mismatch between high-frequency signal sources and nanoscale circuit interfaces. Although topologically protected helical edge modes offer a dissipationless and backscattering-resilient alternative, achieving nanoscale control over these modes requires direct visualization of their spatial electrodynamics, especially under high-frequency operation. Here, by utilizing cryogenic magneto-infrared scattering-type scanning near-field optical microscopy (cm-IR-sSNOM), we image spin-polarized helical edge channels in ZrTe 5 at the nanoscale, revealing magnetic-field-induced brightening as a high-frequency electrodynamic signature of robust topological edge modes. Operating at 1.8 K and under a magnetic field of up to 5 T, we observe the emergence of edge-state polarizability at infrared frequencies that is notably resilient to the magnetic gaps that typically quench d.c. and microwave edge transport. Our results reveal a topological ‘two-lane’ spatial reorganization in which an external magnetic field induces a spin-population imbalance between counterpropagating edge modes. Favoured helical branches are confined against physical boundaries to activate a net infrared near-field contrast. This electrodynamic response scales linearly with the number of atomic layers, which confirms that individual layers in ZrTe 5 preserve their discrete quantum spin Hall identities. These findings may be useful for developing topological spintronic devices, as the magnetic infrared tunability of helical edge channels provides a pathway for low-loss nanoscale interconnects and high-speed information processing.

36 MATERIALS SCIENCE↗