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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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Toward Superb Perovskite Oxide Electrocatalysts: Engineering of Coupled Nanocomposites

Abstract A significant issue that bedeviled the commercialization of renewable energy technologies, ranging from low‐temperature water electrolyzers to high‐temperature solid oxide cells, is the lack of high‐performance catalysts. Among various candidates that could tackle such a challenge, perovskite oxides are rising‐star materials because of their unique structural and compositional flexibility. However, single‐phase perovskite oxides are challenging to satisfy all the requirements of electrocatalysts concurrently for practical applications, such as high catalytic activity, excellent stability, good ionic and electronic conductivities, and superior chemical/thermo‐mechanical robustness. Impressively, perovskite oxides with coupled nanocomposites are emerging as a novel form offering multifunctionality due to their intrinsic features, including infinite interfaces with solid interaction, tunable compositions, flexible configurations, and maximum synergistic effects between assorted components. Considering this new configuration has attracted great attention owing to its promising performances in various energy‐related applications, this review timely summarizes the leading‐edge development of perovskite oxide‐based coupled nanocomposites. Their state‐of‐art synthetic strategies are surveyed and highlighted, their unique structural advantages are highlighted and illustrated through the typical oxygen reduction reaction and oxygen evolution reactions in both high and low‐temperature applications. Opinions on the current critical scientific issues and opportunities in this burgeoning research field are all provided.

08 HYDROGEN↗
DOE OSTI2022

The role of deviatoric stress and dislocations on the α to ω phase transformation in Ti

Under extreme conditions, α-Ti becomes unstable and transforms either into β-Ti at high temperature or into ω-Ti at high pressure. In what concerns the α to ω phase transformation (PT), there has been a wide range of experimentally reported transition pressures from approximately 2 to 15 GPa at room temperature. Deviatoric stresses and internal defects are often assumed to be the root cause of this variation. Here, in this study, these postulates are revisited using both continuum mechanics and molecular dynamics (MD) simulations. First, a simple continuum model, assuming linear elasticity and isotropic plasticity, is developed to describe the effects of applied stress and dislocations on the stability of an ω nucleus in an infinite α domain. Second, a new MD simulation method is developed to generate an ω nucleus in the α domain utilizing the displacement field identified from the topological analysis. Results from MD simulations show that despite the fact that phase diagrams typically delineate the limits between two phases in terms of only P and T, deviatoric stress promotes the α to ω phase transformation by reducing the critical radius above which an ω nucleus is stable. Furthermore, the required deviatoric stress to nucleate and stabilize a nanoscale ω nucleus is likely emanating from the internal stress of defects such as dislocations. The MD-informed micromechanics models are used to identify favorable configurations where dislocations help favor the α to ω transformation. These configurations show that the interaction with a basal or prismatic dislocation reduces the critical radius of a ω nucleus by about 10 or 16 %, respectively. In addition, prismatic edge dislocations are found to promote the growth of ω nucleus when interacting with the ($\bar{1}$$\bar{1}$20) α //(0001) ω interface. Importantly, a simple model of the arrival of dislocation at an ω nucleus suggests that PT does not necessarily require a pile-up to be present but could alternatively be mediated by a constant rapid flow of dislocations.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Disorderly Conduct of Benzamide IV: Crystallographic and Computational Analysis of High Entropy Polymorphs of Small Molecules

Benzamide, a simple derivative of benzoic acid and a common intermediate of pharmaceutical compounds, was reported to form two polymorphs in 1832, but the single crystal structure of the more stable form was not solved until 1959. Nearly 50 years later, the second form was characterized by powder diffraction, followed shortly thereafter by characterization of a third form, a polytype of the most thermodynamically stable Form I. These two new forms, Forms II and III, are metastable. Herein, we describe a fourth polymorph, Form IV, discovered by melt crystallization concurrently with its crystallization under confinement at small length scales (<10 nm), where it is stable indefinitely. Form III exists under confinement in larger pores, and melting point data for different pore sizes corroborate the existence of Form IV below 10 nm. Form IV is highly disordered, precluding indexing of powder diffraction data other than hk0 reflections. Nonetheless, a combination of powder X-ray diffraction and computational crystal structure prediction reveals that Form IV contains a 2D motif resembling that of Form II, but with longrange order in the third dimension masked by ubiquitous stacking faults. This approach relies on distilling a large number of candidate structures to a few possible disorder models based on benzamide tetrads that organize in 2D parquet-like tiles, with organization along the third dimension, that can be modeled with various stacking fault configurations having distinct intermolecular interactions and translations in the dimension orthogonal to the tiling planes. These observations reveal a bewildering crystallographic complexity for such a simple molecule. Nonetheless, the approach described herein demonstrates that challenging structures that may be abandoned prematurely because of poor crystallinity, twinning, or disorder can be solved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Solid-State Calcium-Ion Diffusion in Ca 1.5 Ba 0.5 Si 5 O 3 N 6

Rechargeable batteries based on multivalent working ions are promising candidates for next-generation high-energy-density batteries. Development of these technologies, however, is largely limited by the low diffusion rate of multivalent ions in solid-state materials, thereby necessitating a better understanding of the design principles that control multivalent-ion mobility. We report Ca 1.5 Ba 0.5 Si 5 O 3 N 6 as a potential calcium solid-state conductor and investigate its Ca migration mechanism by means of ab initio computations and neutron diffraction. This compound contains partially occupied Ca sites in close proximity to each other, providing a unique mechanism for Ca migration. Nuclear density maps obtained with the maximum entropy method from neutron powder diffraction data provide strong evidence for low-energy percolating one-dimensional pathways for Ca-ion migration. Ab initio molecular dynamics simulations further support a low Ca-ion migration barrier of ~400 meV when Ca vacancies are present and reveal a unique "vacancy-adjacent"concerted ion migration mechanism. This work provides a new understanding of solid-state Ca-ion diffusion and insights into the future design of novel cation configurations that utilize the interactions between mobile ions to enable fast multivalent-ion conduction in solid-state materials.

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

Discovery of orbital ordering in Bi 2 Sr 2 CaCu 2 O 8+x

The primordial ingredient of cuprate superconductivity is the CuO 2 unit cell. Theories usually concentrate on the intra-atom Coulombic interactions dominating the 3d 9 and 3d 10 configurations of each copper ion. However, if Coulombic interactions also occur between electrons of the 2p 6 orbitals of each planar oxygen atom, spontaneous orbital ordering may split their energy levels. This long-predicted intra-unit-cell symmetry breaking should generate an orbitally ordered phase, for which the charge transfer energy ε separating the 2p 6 and 3d 10 orbitals is distinct for the two oxygen atoms. Here we introduce sublattice-resolved ε(r) imaging to CuO 2 studies and discover intra-unit-cell rotational symmetry breaking of ε(r). Spatially, this state is arranged in disordered Ising domains of orthogonally oriented orbital order bounded by dopant ions, and within whose domain walls low-energy electronic quadrupolar two-level systems occur. Overall, these data reveal a Q = 0 orbitally ordered state that splits the oxygen energy levels by ~50 meV, in underdoped CuO 2 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Shape evolution in even-mass 98-104 Zr isotopes via lifetime measurements using the $\gamma \gamma $-coincidence technique

The Zirconium (Z = 40) isotopic chain has attracted interest for more than four decades. The abrupt lowering of the energy of the first 2 + state and the increase in the transition strength B(E2; 2$^+_1$ →0$^+_1$) going from 98 Zr to 100 Zr has been the first example of “quantum phase transition” in nuclear shapes, which has few equivalents in the nuclear chart. Although a multitude of experiments have been performed to measure nuclear properties related to nuclear shapes and collectivity in the region, none of the measured lifetimes were obtained using the Recoil Distance Doppler Shift method in the γγ-coincidence mode where a gate on the direct feeding transition of the state of interest allows a strict control of systematical errors. Here this work reports the results of lifetime measurements for the first yrast excited states in 98-104 Zr carried out to extract reduced transition probabilities. The new lifetime values in γγ-coincidence and γ-single mode are compared with the results of former experiments. Recent predictions of the Interacting Boson Model with Configuration Mixing, the Symmetry Conserving Configuration Mixing model based on the Hartree–Fock–Bogoliubov approach and the Monte Carlo Shell Model are presented and compared with the experimental data.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Structural and dynamic changes in P-Rex1 upon activation by PIP 3 and inhibition by IP 4

PIP 3 -dependent Rac exchanger 1 (P-Rex1) is abundantly expressed in neutrophils and plays central roles in chemotaxis and cancer metastasis by serving as a guanine-nucleotide exchange factor (GEF) for Rac. The enzyme is synergistically activated by PIP 3 and heterotrimeric Gβγ subunits, but mechanistic details remain poorly understood. While investigating the regulation of P-Rex1 by PIP 3 , we discovered that Ins(1,3,4,5)P 4 (IP 4 ) inhibits P-Rex1 activity and induces large decreases in backbone dynamics in diverse regions of the protein. Cryo-electron microscopy analysis of the P-Rex1·IP 4 complex revealed a conformation wherein the pleckstrin homology (PH) domain occludes the active site of the Dbl homology (DH) domain. This configuration is stabilized by interactions between the first DEP domain (DEP1) and the DH domain and between the PH domain and a 4-helix bundle (4HB) subdomain that extends from the C-terminal domain of P-Rex1. Disruption of the DH–DEP1 interface in a DH/PH-DEP1 fragment enhanced activity and led to a more extended conformation in solution, whereas mutations that constrain the occluded conformation led to decreased GEF activity. Variants of full-length P-Rex1 in which the DH–DEP1 and PH–4HB interfaces were disturbed exhibited enhanced activity during chemokineinduced cell migration, confirming that the observed structure represents the autoinhibited state in living cells. Interactions with PIP 3 -containing liposomes led to disruption of these interfaces and increased dynamics protein-wide. Our results further suggest that inositol phosphates such as IP 4 help to inhibit basal P-Rex1 activity in neutrophils, similar to their inhibitory effects on phosphatidylinositol-3-kinase.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Exploring the nexus of many-body theories through neural network techniques: the tangent model

Abstract In this paper, we present a physically informed neural network (NN) representation of the effective interactions associated with coupled-cluster downfolding models to describe chemical systems and processes. The NN representation not only allows us to evaluate the effective interactions efficiently for various geometrical configurations of chemical systems corresponding to various levels of complexity of the underlying wave functions, but also reveals that the bare and effective interactions are related by a tangent function of some latent variables. We refer to this characterization of the effective interaction as a tangent model. We discuss the connection between this tangent model for the effective interaction with the previously developed theoretical analysis that examines the difference between the bare and effective Hamiltonians in the corresponding active spaces.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Photocrosslinking Probes Proximity of Thymine Modifiers Tethering Excitonically Coupled Dye Aggregates to DNA Holliday Junction

A DNA Holliday junction (HJ) has been used as a versatile scaffold to create a variety of covalently templated molecular dye aggregates exhibiting strong excitonic coupling. In these dye-DNA constructs, one way to attach dyes to DNA is to tether them via single long linkers to thymine modifiers incorporated in the core of the HJ. Here, using photoinduced [2 + 2] cycloaddition (photocrosslinking) between thymines, we investigated the relative positions of squaraine-labeled thymine modifiers in the core of the HJ, and whether the proximity of thymine modifiers correlated with the excitonic coupling strength in squaraine dimers. Photocrosslinking between squaraine-labeled thymine modifiers was carried out in two distinct types of configurations: adjacent dimer and transverse dimer. The outcomes of the reactions in terms of relative photocrosslinking yields were evaluated by denaturing polyacrylamide electrophoresis. We found that for photocrosslinking to occur at a high yield, a synergetic combination of three parameters was necessary: adjacent dimer configuration, strong attractive dye–dye interactions that led to excitonic coupling, and an A-T neighboring base pair. The insight into the proximity of dye-labeled thymines in adjacent and transverse configurations correlated with the strength of excitonic coupling in the corresponding dimers. To demonstrate a utility of photocrosslinking, we created a squaraine tetramer templated by a doubly crosslinked HJ with increased thermal stability. These findings provide guidance for the design of HJ-templated dye aggregates exhibiting strong excitonic coupling for exciton-based applications such as organic optoelectronics and quantum computing.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Controlling Interactions between Quantum Emitters Using Atom Arrays

We investigate the potential for two-dimensional atom arrays to modify the radiation and interaction of individual quantum emitters. Specifically, we demonstrate that control over the emission linewidths, resonant frequency shifts, and local driving field enhancement in impurity atoms is possible due to strong dipole-dipole interactions within ordered, subwavelength atom array configurations. We demonstrate that these effects can be used to dramatically enhance coherent dipole-dipole interactions between distant impurity atoms within an atom array. Possible experimental realizations and potential applications are discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Role of Capping Agents in the Synthesis of Salicylate-Capped Zinc Oxide Nanoparticles

Capping agents are often used for controlling the size, aggregation, and properties of nanoparticles. To guide the design of improved nanomaterials for targeted performance, one can use mechanistic insights into the interactions between capping agents and nanoparticles. Here, we employ density functional theory (DFT), reactive force-field molecular dynamics (ReaxFF MD) simulations, and optical spectroscopy to study the interactions between salicylate, as a model capping agent, and zinc oxide (ZnO) nanoparticles. In this work, we find that salicylate strongly interacts with the nanoparticle via the formation of O–Zn bonds in a distorted six-membered coordination ring structure. We describe the mechanisms of capping of ZnO nanoparticles by salicylate via three different binding modes. Simulations indicate that salicylate undergoes dissociative adsorption at the highly active surface Zn sites via a hydrogen-transfer process, thereby forming a tridentate configuration. The water-mediated interaction also facilitates the dissociative adsorption, leading to two salicylate O atoms coordinating with a surface Zn atom, while the other salicylate O atom bonds with another surface Zn atom. For molecular adsorption, binding free energies indicate that salicylate binds more strongly to ZnO, often in a bidentate configuration, than water does. The formation of the salicylate–ZnO complex is substantiated by UV–visible and Fourier transform infrared spectra. We find that the C=O stretching mode of salicylate becomes softened when it interacts with the nanoparticle, suggesting chemisorption of salicylate on ZnO. Although DFT predicts strong interaction between salicylate and ZnO, ReaxFF MD simulation indicates the moderate interaction between these two components in aqueous solution. Water molecules in close contact with the nanoparticle surface undergo dissociation, thus resulting in a surface hydroxyl, a reactive oxygen species that may influence the nanoparticle’s catalytic properties. Overall, the atomic-level information provided here can guide the selection process of salicylate as an appropriate agent for ZnO nanoparticle synthesis when strong interactions of particles with capping agents are required.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Local Two- and Three-Nucleon Chiral Interactions

We report that understanding the structure and reactions of nuclei from first principles has been a long-standing goal of nuclear physics. In this respect, few- and many-body systems provide a unique laboratory for studying nuclear interactions. In the past couple of decades, the modeling of nuclear interactions has progressed significantly owing, in particular, to the development of chiral effective field theory (χEFT), a low-energy effective representation of quantum chromodynamics (QCD). Within χEFT, many studies have dealt with the construction of both two- and three-nucleon interactions. The aim of the present article is to provide a concise account of chiral interaction models that are local in configuration space, and to report on a selection of recent results for nuclear systems obtained with these interactions.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Electrically tuned hyperfine spectrum in neutral Tb( II )(Cp iPr5 ) 2 single-molecule magnet

Molecular spin qubits with long spin coherence time as well as non-invasive operation methods on such qubits are in high demand. It was shown that both molecular electronic and nuclear spin levels can be used as qubits. In solid state systems with dopants, an electric field was shown to effectively change the spacing between the nuclear spin qubit levels when the electron spin density is high at the nucleus of the dopant. Inspired by such solid-state systems, we propose that divalent lanthanide (Ln) complexes with an unusual electronic configuration of Ln 2+ have a strong interaction between the Ln nuclear spin and the electronic degrees of freedom, which renders electrical tuning of the interaction. Furthermore, as an example, we study electronic structure and hyperfine interaction of the 159 Tb nucleus in a neutral Tb(II)(Cp iPr5 ) 2 single-molecule magnet (SMM), which exhibits unusually long magnetization relaxation time, using the complete active space self-consistent field (CASSCF) method with spin–orbit interaction included within the restricted active space state interaction (RASSI). Our calculations show that the low-energy states arise from 4f 8 (6s,5d z 2 ) 1 , 4f 8 (5d x 2 -y 2 ) 1 , and 4f 8 (5d xy ) 1 configurations. We compute the hyperfine interaction parameters and the electronic–nuclear spectrum within our multiconfigurational approach. We find that the hyperfine interaction is about one order of magnitude greater than that for Tb(III)Pc 2 SMMs. This stems from the strong Fermi contact interaction between the Tb nuclear spin and the electron spin density at the nucleus that originates from the occupation of the (6s,5d) orbitals. We also uncover that the response of the Fermi contact term to electric field results in electrical tuning of the electronic–nuclear level separations. This hyperfine Stark effect may be useful for applications of molecular nuclear spins for quantum computing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Development of aerosol activation in the double-moment Unified Model and evaluation with CLARIFY measurements

Representing the number and mass of cloud and aerosol particles independently in a climate, weather prediction or air quality model is important in order to simulate aerosol direct and indirect effects on radiation balance. Here we introduce the first configuration of the UK Met Office Unified Model in which both cloud and aerosol particles have “double-moment” representations with prognostic number and mass. The GLObal Model of Aerosol Processes (GLOMAP) aerosol microphysics scheme, already used in the Hadley Centre Global Environmental Model version 3 (HadGEM3) climate configuration, is coupled to the Cloud AeroSol Interacting Microphysics (CASIM) cloud microphysics scheme. We demonstrate the performance of the new configuration in high-resolution simulations of a case study defined from the CLARIFY aircraft campaign in 2017 near Ascension Island in the tropical southern Atlantic. We improve the physical basis of the activation scheme by representing the effect of existing cloud droplets on the activation of new aerosol, and we also discuss the effect of unresolved vertical velocities. We show that neglect of these two competing effects in previous studies led to compensating errors but realistic droplet concentrations. While these changes lead only to a modest improvement in model performance, they reinforce our confidence in the ability of the model microphysics code to simulate the aerosol–cloud microphysical interactions it was designed to represent. Capturing these interactions accurately is critical to simulating aerosol effects on climate.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Effect of tert -Butyl Substitution on the Interactions of Cobalt Phthalocyanine with a Carbon Monoxide-Functionalized Tip

Supported cobalt phthalocyanines (CoPc) are promising catalysts for CO 2 reduction, a critical process for mitigating greenhouse gas emissions. Enhancing the catalytic performance of CoPc involves modifying the interaction between the cobalt center and intermediate species. This study focuses on the effects of tert-butyl substitution on CoPc using (tert-butyl) 4 CoPc, where the substitution can both directly alter the molecule’s intramolecular electronic structure and indirectly alter it by the bulky group weakening the interaction with the support. Toward this end, we investigated the structural and chemical properties of (tert-butyl) 4 CoPc on a Ag(111) surface at the single-molecule level using three-dimensional atomic force microscopy (AFM) with a CO-terminated tip and discussed them in comparison with data for unmodified CoPc and amino-substituted CoPc. Notably, distance-dependent force measurements revealed anomalies in the tert-butyl groups’ force curves, attributed to their rotational flexibility. The tert-butyl (t-butyl) groups were also observed to increase the attraction of the central Co atom to CO, but this effect was attributed largely to enhanced interactions of the back of the tip with the peripheral t-butyl groups. In conclusion, while this longer-range interaction would not be expected to impact the interaction of small molecules with the catalytic center, the results reveal the ability of AFM to characterize longer range environmental interactions that can enhance adsorption and subsequent reactions of larger molecules, as well as the role side chains that offer configurational adaptability may play in these interactions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗