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DOE OSTI2026

Reaction Mechanism of Electrodeposited ε-MnO 2 : A Proton-Centered Pathway in Aqueous Zn-Ion Systems

Aqueous Zn/MnO 2 batteries have garnered significant interests owing to their abundance, high theoretical specific capacity, safety, and low cost. However, large-scale application of these systems is limited by the incomplete understanding of the MnO 2 reaction chemistry. The different crystal lattice structures among MnO 2 polymorphs contribute to the variations in reported reaction mechanisms. Among them, ε-MnO 2 polymorph, the dominant phase in electrolytic manganese dioxide (EMD), is notably observed during the charge cycles of aqueous Zn/MnO 2 batteries. Here, in this work, we investigate the electrochemical behavior of an ε-MnO 2 cathode synthesized via electrodeposition from a ZnSO 4 and MnSO 4 electrolyte, onto a 3-dimensional carbon cloth substrate. Proton intercalation emerges as the dominant charge storage mechanism, critically enabling the reversibility of ε-MnO 2 during cycling, as revealed by operando synchrotron X-ray diffraction and X-ray absorption spectroscopy. Additionally, a proton-coupled dissolution/redeposition pathway operates alongside minor Zn 2+ intercalation, as quantified by Rietveld refinement. Morphological and chemical heterogeneities are studied by transmission X-ray microscopy further validates this reaction mechanism. These mechanistic insights provide the foundation for rationally designing Zn/MnO 2 batteries with optimized proton dynamics and charge transfer, advancing these systems as a viable solution for safe, cost-effective grid-scale energy storage.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Improved Representations of Longwave Surface Emissivity to Reduce Surface and Atmospheric Heating Biases in Earth System Models

Abstract Many Earth system models (ESMs) approximate surface emissivity as a broadband constant. This approximation reduces the computational burden, yet omits the spectral structure of emissivity and atmospheric absorption. Neglecting spectral variation in surface emission introduces biases in longwave (LW) atmospheric fluxes and heating. Biases are strongest over surfaces with strongly varying emissivity and minimal atmospheric opacity. We examine these biases over water, ice, and snow surfaces. We partition spectral emissivity into the 16 spectral bands utilized by a single‐column atmospheric radiative transfer model (RRTMG_LW) commonly used in ESMs. We quantify flux and heating biases introduced by broadband assumptions relative to the spectrally resolved case for standard atmospheric profiles over each surface type. Current assumptions tend to overestimate upwelling surface fluxes; for example, the greybody assumption overestimates flux by 1.6 W/m 2 (0.52%) at the bottom of a mid‐latitude winter atmosphere over ice, and by 2.33 (1.0%) at the top of atmosphere. The blackbody assumption tends to artificially cool Earth's surface, stabilizing the lower troposphere. Interestingly, the optimal broadband emissivity can deviate from the Planck‐weighted mean by up to 3% depending on surface type and atmospheric profile. We investigate bias sensitivity to surface temperature, cloud water path, and atmospheric water vapor. Bias is most sensitive to water vapor content, and least sensitive to cloud water path. Lastly, we show that a modified greybody method with updated broadband values can reduce total surface flux bias up to 1.69 , comparable to a five‐band approach and at a fraction of the computational cost.

Manzo, L. [Department of Earth System Science Univ↗

DOE OSTI2020

A measurement of the equation of state of carbon envelopes of white dwarfs

White dwarfs represent the final state of evolution for most stars. Certain classes of white dwarfs pulsate, leading to observable brightness variations, and analysis of these variations with theoretical stellar models probes their internal structure. Modelling of these pulsating stars provides stringent tests of white dwarf models and a detailed picture of the outcome of the late stages of stellar evolution. However, the high-energy-density states that exist in white dwarfs are extremely difficult to reach and to measure in the laboratory, so theoretical predictions are largely untested at these conditions. In this paper we report measurements of the relationship between pressure and density along the principal shock Hugoniot (equations describing the state of the sample material before and after the passage of the shock derived from conservation laws) of hydrocarbon to within five per cent. The observed maximum compressibility is consistent with theoretical models that include detailed electronic structure. This is relevant for the equation of state of matter at pressures ranging from 100 million to 450 million atmospheres, where the understanding of white dwarf physics is sensitive to the equation of state and where models differ considerably. The measurements test these equation-of-state relations that are used in the modelling of white dwarfs and inertial confinement fusion experiments, and we predict an increase in compressibility due to ionization of the inner-core orbitals of carbon. We also find that a detailed treatment of the electronic structure and the electron degeneracy pressure is required to capture the measured shape of the pressure–density evolution for hydrocarbon before peak compression. Our results illuminate the equation of state of the white dwarf envelope (the region surrounding the stellar core that contains partially ionized and partially degenerate non-ideal plasmas), which is a weak link in the constitutive physics informing the structure and evolution of white dwarf stars.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2021

Quantification of Dissolved O 2 in Bulk Aqueous Solutions and Porous Media Using NMR Relaxometry

Effects of dissolved paramagnetic oxygen (O 2 ) in water on 1 H nuclear magnetic resonance (NMR) Carr-Purcell-Meiboom-Gill (CPMG) experiments is evaluated at a 1 H Larmor frequency of 2 MHz. Dissolution of O 2 into water significantly reduces the 1 H transverse relaxation coefficient (T 2 ). For deoxygenated water, T 2 is 3388 ms, water at ambient atmospheric conditions (7.4 mg/L O2) exhibits a T2 of 2465 ms, and dissolution of 2710 mg/L O 2 further reduces T 2 to 36 ms. The results were fit with an empirical model to facilitate prediction of T 2 times for bulk water as a function of paramagnetic oxygen concentrations in solution. Dissolved O 2 also greatly influences 1 H NMR CPMG experiments of confined water in a model system composed of Berea sandstone. For this system, 90 mg/L O 2 in H 2 O enhances T 2 relaxation of bulk water such that the relaxation time is comparable to physically confined water in the sandstone pores. Given the sensitivity of NMR T 2 coefficients to paramagnetic oxygen, low-field NMR-based characterization of fluid and porous media structure requires control of dissolved oxygen, as geospatial variation in the partial pressure of O 2 alone is expected to perturb fluid and pore relaxation times by up to 60 and 36%, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

The minor pilin PilV provides a conserved adhesion site throughout the antigenically variable meningococcal type IV pilus

Type IV pili (T4P) are among the most widespread adhesive factors in prokaryotes. In pathogenic Neisseria, the major pilin, which provides the structural framework for the filamentous T4P, undergoes antigenic variation allowing the bacteria to evade the humoral immune response without impacting host-cell adhesion. Here, we show that a minor pilin, PilV, is distributed throughout the pilus and contributes to Neisseria meningitidis adhesion and that antibodies to PilV block meningococcal adhesion in vivo. Our results provide a mechanism whereby N. meningitidis varies its immunodominant major pilin to escape antibody recognition while maintaining conserved sites throughout the pilus for host receptor binding. They further suggest a strategy to prevent or block deadly N. meningitidis infections by targeting this minor pilin.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2025

The Atacama Cosmology Telescope: DR6 constraints on extended cosmological models

We use new cosmic microwave background (CMB) primary temperature and polarization anisotropy measurements from the Atacama Cosmology Telescope (ACT) Data Release 6 (DR6) to test foundational assumptions of the standard cosmological model, ΛCDM, and set constraints on extensions to it. We derive constraints from the ACT DR6 power spectra alone, as well as in combination with legacy data from the Planck mission. To break geometric degeneracies, we include ACT and Planck CMB lensing data and baryon acoustic oscillation data from DESI Year-1. To test the dependence of our results on non-ACT data, we also explore combinations replacing Planck with WMAP and DESI with BOSS, and further add supernovae measurements from Pantheon+ for models that affect the late-time expansion history. We verify the near-scale-invariance (running of the spectral index dn s /d ln k = 0.0062 ± 0.0052) and adiabaticity of the primordial perturbations. Neutrino properties are consistent with Standard Model predictions: we find no evidence for new light, relativistic species that are free-streaming (N eff = 2.86 ± 0.13, which combined with astrophysical measurements of primordial helium and deuterium abundances becomes N eff = 2.89 ± 0.11), for non-zero neutrino masses (∑m ν < 0.089 eV at 95% CL), or for neutrino self-interactions. We also find no evidence for self-interacting dark radiation (N idr < 0.134), or for early-universe variation of fundamental constants, including the fine-structure constant (α EM /α EM,0 = 1.0043 ± 0.0017) and the electron mass (m e /m e,0 = 1.0063 ± 0.0056). Our data are consistent with standard big bang nucleosynthesis (we find Y p = 0.2312 ± 0.0092), the COBE/FIRAS-inferred CMB temperature (we find T CMB = 2.698 ± 0.016 K), a dark matter component that is collisionless and with only a small fraction allowed as axion-like particles, a cosmological constant (w = -0.986 ± 0.025), and the late-time growth rate predicted by general relativity (γ = 0.663 ± 0.052). We find no statistically significant preference for a departure from the baseline ΛCDM model. In fits to models invoking early dark energy, primordial magnetic fields, or an arbitrary modified recombination history, we find H 0 = 69.9 +0.8 -1.5 , 69.1 ± 0.5, or 69.6 ± 1.0 km/s/Mpc, respectively; using BOSS instead of DESI BAO data reduces the central values of these constraints by 1–1.5 km/s/Mpc while only slightly increasing the error bars. In general, models introduced to increase the Hubble constant or to decrease the amplitude of density fluctuations inferred from the primary CMB are not favored over ΛCDM by our data.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2024

Preserving isohydricity: vertical environmental variability explains Amazon forest water-use strategies

Abstract Increases in hydrological extremes, including drought, are expected for Amazon forests. A fundamental challenge for predicting forest responses lies in identifying ecological strategies which underlie such responses. Characterization of species-specific hydraulic strategies for regulating water-use, thought to be arrayed along an ‘isohydric–anisohydric’ spectrum, is a widely used approach. However, recent studies have questioned the usefulness of this classification scheme, because its metrics are strongly influenced by environments, and hence can lead to divergent classifications even within the same species. Here, we propose an alternative approach positing that individual hydraulic regulation strategies emerge from the interaction of environments with traits. Specifically, we hypothesize that the vertical forest profile represents a key gradient in drought-related environments (atmospheric vapor pressure deficit, soil water availability) that drives divergent tree water-use strategies for coordinated regulation of stomatal conductance (gs) and leaf water potentials (ΨL) with tree rooting depth, a proxy for water availability. Testing this hypothesis in a seasonal eastern Amazon forest in Brazil, we found that hydraulic strategies indeed depend on height-associated environments. Upper canopy trees, experiencing high vapor pressure deficit (VPD), but stable soil water access through deep rooting, exhibited isohydric strategies, defined by little seasonal change in the diurnal pattern of gs and steady seasonal minimum ΨL. In contrast, understory trees, exposed to less variable VPD but highly variable soil water availability, exhibited anisohydric strategies, with fluctuations in diurnal gs that increased in the dry season along with increasing variation in ΨL. Our finding that canopy height structures the coordination between drought-related environmental stressors and hydraulic traits provides a basis for preserving the applicability of the isohydric-to-anisohydric spectrum, which we show here may consistently emerge from environmental context. Our work highlights the importance of understanding how environmental heterogeneity structures forest responses to climate change, providing a mechanistic basis for improving models of tropical ecosystems.

Forestry↗

DOE OSTI2024

Composition dependence of bulk properties in the Co-intercalated transition metal dichalcogenide $\mathrm{Co_{1/3}TaS_2}$

Spontaneous Hall conductivity has recently been reported in the triangular lattice antiferromagnet Co 1/3 TaS 2 under a zero magnetic field. This phenomenon originates from the distinctive noncoplanar triple-Q magnetic ground state, possessing uniform real-space Berry curvature characterized by scalar spin chirality. We investigated the physical properties of Co 1/3 TaS 2 by judiciously controlling the composition, revealing a drastic change in its bulk properties, even by slight variations in cobalt composition, despite the same crystal structure. For 0.299≤x≤0.325, Co x TaS 2 keeps all the characteristics of the ground state consistent with the previous studies—two antiferromagnetic phase transitions at T N1 and T N2 ( N1 ), a large spontaneous Hall conductivity [σ xy (H=0)], and a weak ferromagnetic moment along the c axis. However, samples with x≥0.330 exhibit distinct bulk properties, including the absence of both σ xy (H=0) and the weak ferromagnetic moment. Our neutron diffraction data reveal that Co x TaS 2 with x≥0.330 develops coplanar helical magnetic order with q m1 =(1/3, 0, 0). This is entirely different from what has been seen in x≤0.325, explaining the observed composition dependence.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2026

Imaging surface topography with coherent x-ray reflectivity: Theory, kinematics, and simulations

A theoretical formalism is described for understanding coherent x-ray reflectivity (CXR) from the surface of a semi-infinite crystal having a variable surface topography, described by the height profile ℎ(𝑥,𝑦). The surface topography is imaged as a complex “effective density,” obtained from the phasing and inversion of the coherent x-ray reflectivity data, measured through a rocking scan centered at a vertical momentum transfer 𝑄$^{0}_{𝑧}$ and a vertical range Δ⁢𝑄 𝑧 . The formalism predicts that the effective density has an amplitude with a maximum located at the surface height for each position within the surface plane. The phase of the effective density has a lateral variation that is controlled by the surface height and a vertical variation that reflects a combination of the interfacial structure and specific choice of measurement conditions. This understanding enables direct observation of nanometer-scale interfacial topography, i.e., ℎ⁡(𝑥,𝑦)⁢𝑐 𝑠 (where 𝑐 𝑠 is the vertical substrate lattice parameter) with Å-scale sensitivity to surface height. Numerical simulations illustrate and confirm the theoretical results. These results show how the interpretation of the interfacial density phase obtained by CXR data inversion (i.e., surface topography with respect to a flat surface) is conceptually similar to that previously known for Bragg coherent diffraction imaging (BCDI) measurements of isolated nanoparticles (i.e., lattice displacements with respect to an ideal crystal lattice). This suggests that CXR can be thought of as a form of dark field imaging with respect to the bright field BCDI approach. An implication of these results is that interfacial imaging may bypass some of the significant challenges associated with BCDI imaging of multiple particles having different orientations.

X-ray imaging↗

DOE OSTI2024

Efficacious Qubit Mappings for Quantum Simulations of the 12 C Rotational Band

Solving atomic nuclei from first principles places enormous demands on computational resources, which grow exponentially with increasing number of particles and the size of the space they occupy. We present first quantum simulations based on the variational quantum eigensolver for the low-lying structure of the 12C nucleus that provide acceptable bound-state energies even in the presence of noise. Here, we achieve this by taking advantage of two critical developments. First, we utilize an almost perfect symmetry of atomic nuclei that, in a complete symmetry-adapted basis, drastically reduces the size of the model space. Second, we use the efficacious Gray encoding, for which it has been recently shown that it is resource efficient, especially when coupled with a near band-diagonal structure of the nuclear Hamiltonian.

Encoding↗

DOE OSTI2021

Intermittent Frontogenesis in the Alboran Sea

Abstract We present a phenomenological description and dynamical analysis of the Alboran fronts using a realistic simulation at submesoscale resolution. The study is focused on east Alboran fronts emerging within relatively strong flows that separate from the Spanish coast into the basin interior. Despite modest lateral shifting associated with the position of the Alboran anticyclonic gyres and variations in intensity, these fronts present a similar structure and dynamical configuration as the climatological Almeria–Oran front. The statistical analysis of our solution shows that strained-induced frontogenesis is a recurrent submesoscale mechanism associated with these fronts, and the process is assessed in terms of the advective Lagrangian frontogenetic tendencies associated with buoyancy and velocity horizontal gradients. Intermittency in their strength and patterns is indicative of high variability in the occurrence of active frontogenesis in association with the secondary (overturning) circulation across the frontal gradient. As a result, we find many episodes with strong surface fronts that do not have much associated downwelling. Frontogenesis and the associated secondary circulation are further explored during two particular frontal events, both showing strong downwelling of (1) cm s −1 extending down into the pycnocline. A frontogenetic contribution of turbulent vertical momentum mixing to the secondary circulation is identified in the easternmost region during the cold season, when the dynamics are strongly influenced by the intrusion of the salty Northern Current. The background vertical velocity fields observed during the analyzed events indicate other currents in the submesoscale range, including tidal and topographic internal waves.

Capó, Esther↗

DOE OSTI2025

VitriEdge: Repairable & Durable Vitrimer Coatings for Wind Turbine Blade Leading Edges

The primary goal of this Level 1b incubator project was to explore the use of vitrimer coatings for repair of leading-edge erosion on end-of-life wind turbine blade surfaces, beyond coating strength of adhesion which has previously been demonstrated in the Level 1a project. Uniform vitrimer coatings (thickness: 400 µm) were applied to two end-of-life wind turbine blades for flexural, fatigue, and laminate tensile testing where the addition of the coating did not produce any statistical variation in tensile properties with minor drops in flexural strength for some laminate formulations. However, a <2% variation in storage modulus was measured for laminate structures (i.e., blade samples with vitrimer coatings) across 100,000 flexural cycles and upon laminate tensile failure, the vitrimer coatings displayed no visible signs of delamination. In addition, three methods to heal vitrimer coating damage was displayed: oven heating, addition of hot water, and a forced convection heat gun. All three heating and healing mechanisms demonstrated significant healing with scratch depths decreasing between 79-91% at healing times ranging between 1-min and 10-minutes. Finally, a water jet machine was used to simulate rain erosion for both the blade surfaces and vitrimer-coated blade surfaces where the diameter and depth of the damage was recorded as a function of exposure time, water pressure, height of exposure, and angle of exposure. Of interest, while the vitrimer coating did not significantly lessen the damage experienced during rain erosion, the addition of vitrimer composite coatings(5 wt.% mica addition) did result in a crack-resistant, durable coating capable of self-healing behavior and in all cases the angle of rain exposure was the most critical parameter explored. It is crucial to continue exploring this space where vitrimer coatings are of interest for both their self-healing properties and potential use as reversible adhesives.

17 WIND ENERGY↗

DOE OSTI2022

Deep Generative Models for Materials Discovery and Machine Learning-Accelerated Innovation

Machine learning and artificial intelligence (AI/ML) methods are beginning to have significant impact in chemistry and condensed matter physics. For example, deep learning methods have demonstrated new capabilities for high-throughput virtual screening, and global optimization approaches for inverse design of materials. Recently, a relatively new branch of AI/ML, deep generative models (GMs), provide additional promise as they encode material structure and/or properties into a latent space, and through exploration and manipulation of the latent space can generate new materials. These approaches learn representations of a material structure and its corresponding chemistry or physics to accelerate materials discovery, which differs from traditional AI/ML methods that use statistical and combinatorial screening of existing materials via distinct structure-property relationships. However, application of GMs to inorganic materials has been notably harder than organic molecules because inorganic structure is often more complex to encode. In this work we review recent innovations that have enabled GMs to accelerate inorganic materials discovery. We focus on different representations of material structure, their impact on inverse design strategies using variational autoencoders or generative adversarial networks, and highlight the potential of these approaches for discovering materials with targeted properties needed for technological innovation.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Antarctic Soils Select Copiotroph-Dominated Bacteria

The life strategies of bacterial communities determine their structure and function and are an important driver of biogeochemical cycling. However, the variations in these strategies under different soil resource conditions remain largely unknown. We explored the bacterial life strategies and changes in structure and functions between Antarctic soils and forest (temperate, subtropical, and tropical) soils. The results showed that the weighted mean rRNA operon copy number in temperate soils was 19.5% lower than that in Antarctic soils, whereas no significant differences were observed among Antarctic, subtropical, and tropical soils. An unexpected result was that bacterial communities in Antarctic soils tended to be copiotrophs, such as Actinobacteriota and Bacteroidota, whereas those in temperate soils tended to be oligotrophs, such as Acidobacteriota and Chloroflexi. Functional predictions showed that in comparison to copiotrophs in Antarctic soils, temperate-inhabiting oligotrophic bacteria exhibited an 84.2–91.1% lower abundance of labile C decomposition genes (hemicellulose, cellulose, monosaccharides, and disaccharides), whereas a 74.4% higher abundance of stable C decomposition (lignin). Genes involved in N cycling (nitrogen fixation, assimilatory nitrate reduction, and denitrification) were 24.3–64.4% lower in temperate soils than in Antarctic soils. Collectively, our study provides a framework for describing the life strategies of soil bacteria, which are crucial to global biogeochemical cycles.

Microbiology↗

DOE OSTI2024

Bi-fidelity variational auto-encoder for uncertainty quantification

Quantifying the uncertainty of quantities of interest (QoIs) from physical systems is a primary objective in model validation. However, achieving this goal entails balancing the need for computational efficiency with the requirement for numerical accuracy. To address this trade-off, we propose a novel bi-fidelity formulation of variational auto-encoders (BF-VAE) designed to estimate the uncertainty associated with a QoI from low-fidelity (LF) and high-fidelity (HF) samples of the QoI. Here, this model allows for the approximation of the statistics of the HF QoI by leveraging information derived from its LF counterpart. Specifically, we design a bi-fidelity auto-regressive model in the latent space which is integrated within the VAE’s probabilistic encoder–decoder structure. An effective algorithm is proposed to maximize the variational lower bound of the HF log-likelihood in the presence of limited HF data, resulting in the synthesis of HF realizations with a reduced computational cost. Additionally, we introduce the concept of the bi-fidelity information bottleneck (BF-IB) to provide an information-theoretic interpretation of the proposed BF-VAE model. Our numerical results demonstrate that the BF-VAE leads to considerably improved accuracy, as compared to a VAE trained using only HF data, when limited HF data is available.

42 ENGINEERING↗

DOE OSTI2024

Stacking disorder and thermal transport properties of α-RuCl 3

α-RuCl 3 , a well-known candidate material for Kitaev quantum spin liquid, is prone to stacking disorder due to the weak van der Waals bonding between the honeycomb layers. After a decade of intensive experimental and theoretical studies, the detailed correlation between stacking degree of freedom, structure transition, magnetic, and thermal transport properties remains unresolved. In this work, we reveal the effects of a small amount of stacking disorder inherent even in high quality α-RuCl 3 crystals. This small amount of stacking disorder results in the variation of the magnetic ordering temperature, and it suppresses the structure transition and thermal conductivity. Crystals with a minimal amount of stacking disorder have a T N > 7.4 K and exhibit a well-defined structure transition around 140 K upon cooling. For those with more stacking faults and a T N below 7 K, the structure transition occurs well below 140 K upon cooling and is incomplete, manifested by the diffuse streaks and the coexistence of both high-temperature and low-temperature phases down to the lowest measurement temperature. Both types of crystals exhibit oscillatory field-dependent thermal conductivity and a plateaulike feature in thermal Hall resistivity in the field-induced quantum spin liquid state. However, α-RuCl 3 crystals with a minimal amount of stacking disorder have a higher thermal conductivity that pushes the thermal Hall conductivity to be closer to the half-integer quantized value. Importantly, these findings demonstrate a strong correlation between layer stacking, structure transition, magnetic, and thermal transport properties, underscoring the importance of interlayer coupling in α-RuCl3 despite the weak van der Waals bonding.

36 MATERIALS SCIENCE↗

DOE OSTI2023

The Zintl Concept Applied to Intergrowth Structures: Electron‐Hole Matching, Stacking Preferences, and Chemical Pressures in Pd 5 InAs

Abstract Enumerating the potential stacking sequences of layers is a fundamental way to account for the structure diversity of solid state compounds. In many cases, these stacking variations represent polymorphs with only small energetic differences. Here, we examine a compound for which the preferred stacking pattern instead reveals key aspects about its chemical bonding: Pd 5 InAs. Its structure is based on the intergrowth of slabs of the AuCu 3 and PtHg 2 (or alternatively, fluorite) structure types. Two basic stacking arrangements are available to this compound, represented by the Pd 5 TlAs and HoCoGa 5 structure types. DFT total energy calculations reveal that the former outcompetes the latter by a staggering 0.65 eV/formula unit. Through a combination of DFT‐reversed approximation Molecular Orbital (DFT‐raMO) and DFT‐Chemical Pressure (DFT‐CP) analysis we trace this preference to two factors. First, with DFT‐raMO analysis, we derive a Zintl‐like bonding scheme of Pd 5 InAs. This scheme, along with the inspection of selected crystal orbitals, is then connected to preferred stacking through the coordination environments of the Pd atoms at the interface between the Pd−In and Pd−As layers. In the hypothetical HoCoGa 5 ‐type and observed Pd 5 InAs‐type structures, different Pd coordination environments arise at the interfaces. The hypothetical structure features square planar PdIn 2 As 2 units, in each of which the same 4d‐orbital serves in the Pd sublattice's role as both Lewis acid (for interactions with the As) and Lewis base (for interactions with the In). In the observed structure, tetrahedral PdIn 2 As 2 units occur instead, so that these contradictory roles are distributed to separate 4d‐orbitals, leading to more effective bonding. DFT‐CP analysis illustrates that this driving force for the Pd 5 TlAs‐type arrangement is supplemented by a favorable alignment of the packing tensions in the parent structures. Altogether, the resulting picture demonstrates how the reaction of simple intermetallic structures to form intergrowths can be guided by recognizable chemical interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Two-Component Multireference Restricted Active Space Configuration Interaction for the Computation of L-Edge X-ray Absorption Spectra

X-ray absorption spectroscopy is a powerful probe of local electronic and nuclear structure, providing insights into chemical processes. The theoretical prediction and interpretation of metal L-edge X-ray absorption spectra is complicated by both relativistic effects, including spin-orbit coupling, and by the multiconfigurational nature of the states involved. This work details an exact two-component multireference restricted active space configuration interaction (X2C-MRRASCI) scheme that uses an exact two-component state average complete active space self-consistent-field method (X2C-SA-CASSCF), which includes the spin-orbit coupling in a variational manner, for the accurate description of the electronic structure before using a restricted active space configuration interaction method to describe the core excited states of the X-ray spectrum. Benchmark calculations are presented for a series of iron containing complexes, with results showing key features of the spectrum being reproduced, including ligand to metal charge transfer and shake-up excitations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗