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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

1D Magnetic MX 3 Single-Chains (M = Cr, V and X = Cl, Br, I)

Magnetic materials in reduced dimensions are not only excellent platforms for fundamental studies of magnetism, but they play crucial roles in technological advances. The discovery of intrinsic magnetism in monolayer 2D van der Waals systems has sparked enormous interest, but the single-chain limit of 1D magnetic van der Waals materials has been largely unexplored. This paper reports on a family of 1D magnetic van der Waals materials with composition MX 3 (M = Cr, V, and X = Cl, Br, I), prepared in fully-isolated fashion within the protective cores of carbon nanotubes. Atomic-resolution scanning transmission electron microscopy identifies unique structures that differ from the well-known 2D honeycomb lattice MX 3 structure. Density functional theory calculations reveal charge-driven reversible magnetic phase transitions.

1D materials↗
DOE OSTI2024

Polymer Passivated All Inorganic Micro‐Structured CsPbI x Br y Perovskite Toward Highly Efficient Photodetectors

Abstract Solution‐processed inorganic perovskites cause chemical and structural defects unfavorable for photodetector application. Using a binary solvent, defects in CsPbI x Br y (CPIB) perovskite are passivated with poly 4‐vinylpyridine (PVP) and Poly methyl methacrylate (PMMA) polymers. X‐ray photoelectron spectroscopy and FTIR spectra reveal a Lewis base‐acid interaction between Pb 2+ and polymer, confirming the passivation of CPIB perovskite. Scanning electron microscopy analysis shows a dual‐surface morphology with microribbons and microcrystals in perovskites. After PMMA treatment, CPIB perovskite exhibits a blue shift in the bandgap (1.8 to 1.95 eV), while the PVP induced a redshift, reducing the bandgap to 1.7 eV. Blue shift in PL analysis indicates modification of grain boundaries. A higher lifetime obtained for CPIB/PVP confirms the restraint of non‐radiative recombinations. Photodetectors are fabricated with pristine CPIB, CPIB/PVP, and CPIB/PMMA perovskites. The passivated CPIB/PVP‐based photodetector exhibits a quick rise time of ≈23 ms and a decay time of ≈17 ms. It also demonstrates a remarkable photoresponsivity of 23 mA W −1 , an internal quantum efficiency of 4.9%, and a detectivity of 15.0 × 10 10 Jones at 10 mW cm −2 light intensity. This approach shows the potential for environmentally stable polymers to passivate inorganic perovskites for high photodetection performance.

Shah, Shruti↗
DOE OSTI2023

Impact of indirect CP violation on Br( K S → μ + μ – ) ℓ=0

The decay K S → μ + μ – ) ℓ=0 , with the final muon pair in an angular-momentum zero state, is a sensitive probe of short-distance physics. It has recently been shown how to extract this branching ratio from neutral kaon decay data. We point out that the impact of indirect CP violation on the standard-model prediction of this mode, while nominally of order $\vert$ε K $\vert$ ~ 10 -3 , is enhanced by a large amplitude ratio and leads to a shift of the branching ratio Br( K S → μ + μ – ) ℓ=0 by a few percent, depending on the size of a relative phase that can be extracted from data. We also update the standard-model prediction of the short-distance contribution.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Influence of ion site occupancies on the unit cell parameters, specific volumes, and densities of M 8 (AlSiO 4 ) 6 X 2 sodalites where M = Li, Na, K, Rb, and Ag and X = Cl, Br, and I

Here, this paper discusses the effects of composition on the unit cell parameter (a), unit cell volume (V), specific volume (v), and density (ρ) of various sodalite compositions including $M^+_8$(AlSiO 4 ) 6 Cl 2 (M = Li, Na, K, Rb, and/or Ag) and Na8(AlSiO 4 ) 6 $X^-_2$(X = Cl, Br, and/or I). Compositional models were developed, and the results show that the models are successful at predicting a, V, and v (and thus ρ) within the compositional range available in the literature. Discussion is included on the correlation between the ionic radii of the alkali metals and halides in the sodalite β-cages and the measured values of a, V, v, and ρ. The data show linear increases in a and ρ with increases in the average ionic radii of the M + and X - constituents (data for v show a linear decrease).

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

Determining P, S, Br, and I content in uranium by triple quadrupole inductively coupled plasma mass spectrometry

The trace impurities of a uranium ore concentrate (UOC) can be examined to determine mine source, methods of production, and quality. This study presents a method to determine the concentration of halides and main group elements, specifically P, S, Br and I, utilizing triple quadrupole inductively coupled plasma–mass spectrometry. These analytes were measured in a uranium matrix to simulate a UOC sample. The concentrations determined with this method showed agreement with known values. Solutions with and without uranium were compared. A UOC certified reference material, CUP-2, was analyzed to further demonstrate the effectiveness of the method.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Thermodynamics of cesium lead halide (CsPbX 3 , x= I, Br, Cl) perovskites

Inorganic cesium lead halide (CsPbX 3 , X = I, Br, Cl) perovskites have sparked broad interest for photovoltaic applications, which, however, may be plagued by chemical and thermodynamic instabilities. This work reports calorimetric studies on the formation enthalpies of CsPbX 3 perovskites, confirming decreasing thermodynamic stability in the order CsPbCl 3 , CsPbBr 3 and CsPbI 3 . Cesium lead iodide (CsPbI 3 ), one of the most studied inorganic lead halide perovskites, is shown to be only barely stable from a thermodynamic perspective. This order of increasing instability is consistent with the variation of Goldschmidt tolerance factor. The perovskites are high temperature entropy-stabilized phases with respect to low temperature polymorphs, with the thermodynamics of phase transitions reflecting the above thermodynamic trends.

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

K 2 CuX 3 (X = Cl, Br): All-Inorganic Lead-Free Blue Emitters with Near-Unity Photoluminescence Quantum Yield

Recently, copper(I) halides have been gaining increased attention as highly luminescent nontoxic alternatives to lead halide perovskites for optoelectronic applications. In this paper, we report preparation of blue emitting, lead free, all-inorganic halides K 2 CuX 3 (X = Cl, Br) through five synthetic methods including traditional solid-state and solution methods. The photoluminescence (PL) emission spectra of K 2 CuCl 3 and K 2 CuBr 3 exhibit narrow peaks centered at 392 and 388 nm with full widths at half-maximum (fwhm) values of ~54 nm. The visible bright blue emission is corroborated by the remarkably high photoluminescence quantum yield (PLQY) values up to ~97%. Furthermore, radioluminescence measurements on K 2 CuCl 3 yield a bright peak at 404 nm under irradiation with X-rays at 200 kVp and 20 mA, which is optimal for use with PMTs and Si photomultipliers, suggesting a strong potential of this family for radiation detection applications. Based on our combined experimental and computational investigations, the origin of the efficient luminescence in K 2 CuX 3 is attributed to the high stability self-trapped excitons (STE) formed in the one-dimensional anionic ∞ 1 [CuX 3 ] 2– chains. Advantageously, K 2 CuX 3 demonstrate improved air- and photostability compared to the previously reported copper(I) halides. The discovery of highly efficient and high stability light emitters based on earth-abundant copper(I) halides paves the way for their potential practical applications.

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

Stabilization of [(N 5 ) 2 BX] 2– and [(N 5 ) 2 B 2 X 2 ] 2– (X = H, F, Cl, Br) by Conjugation and Hyperconjugation Effects

The isolation of nucleophilic boron bases has led to a paradigm shift in boron chemistry. Previous studies of the bis(carbene) borylene complexes revealed that these compounds possess strong donor abilities, and their reaction inertness is due to the large steric hindrance between boron reagents and reactant. In the present study, we have theoretically studied the [(N 5 ) 2 BX] 2– and [(N 5 ) 2 B 2 X 2 ] 2– compounds (X = H, F, Cl, Br). Their electronic structures and properties are discussed by using the NBO, LOL, and ELF methods. We found that both π-conjugation and hyperconjugation effects can effectively stabilize the substituted nucleophilic anionic boron compounds [(N 5 ) 2 BX] 2– and [(N 5 ) 2 B 2 X 2 ] 2– . Substituents, especially X = H, stabilize the boron center through highly delocalized π-bonding, involving the formally “empty” in-plane p orbitals of the boron atom. While the halogen substituents have high electron withdrawal ability, leading to systems being less stable, we suggest the borinium anions [(N 5 ) 2 BH] 2– and [(N 5 ) 2 B 2 H 2 ] 2– as possible synthetic targets of novel environmentally friendly catalysts.

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

Bond Dissociation Energies and Electronic Calculations on the Actinide Halides ThX and UX (X = Cl, Br, I)

Resonant two-photon ionization spectroscopy has been used to locate predissociation thresholds in the spectra of the actinide halides ThX and UX, where X = Cl, Br, and I. These predissociation thresholds are identified as the bond dissociation energies (BDEs) of the molecules. The resulting values show very similar BDEs for the corresponding ThX and UX species, with the thorium molecules being slightly more strongly bound: D 0 (ThCl) = 5.077(6) eV, D 0 (ThBr) = 4.391(4) eV, D 0 (ThI) = 3.537(8) eV, D 0 (UCl) = 4.989(3) eV, D 0 (UBr) = 4.313(3) eV, and D 0 (UI) = 3.449(8) eV. Here, the estimated error limit is given in parentheses in units of the last reported digit. Spinor-based coupled cluster calculations have also been carried out on the halides of this work, including also ThF and UF. Here, the final D 0 values after including contributions due to basis set incompleteness, outer-core-correlation, picture-change, and QED effects are within 0.04 eV of the present experimental values in each case.

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

Large Electrically and Chemically Tunable Rashba–Dresselhaus Effects in Ferroelectric CsGeX 3 (X = Cl, Br, I) Perovskites

Rashba–Dresselhaus effects, which originate from spin–orbit coupling and allow for spin manipulations, are actively explored in materials, following the pursuit of spintronics and quantum computing. However, materials that possess practically significant Rashba–Dresselhaus effects often contain toxic elements and offer little opportunity for the tunability of the effects. We used first-principles simulations to reveal that the recently discovered halide ferroelectrics in the CsGeX 3 (X = Cl, Br, I) family possess large and tunable Rashba-Dresselhaus effects. In particular, they give origin to the spin splitting of up to 171 meV in the valence band of CsGeI 3 . The value is chemically tunable and can decrease by 25% and 70% for CsGeBr 3 and CsGeCl 3 , respectively. Such chemical tunability could result in the engineering of desired values through a solid solution technique. Application of an electric field was found to result in structural changes that could decrease and increase spin splitting, leading to electrical tunability of the effect. In the vicinity of conduction and valence band extrema, the spin textures are mostly of the Rashba type, which is promising for spin-to-charge conversion applications. The spin directions are coupled with the polarization direction, leading to Rashba-ferroelectricity cofunctionality. Furthermore, our work identifies lead-free perovskite halides as excellent candidates for spin-based applications and is likely to stimulate further research in this direction.

Electric fields↗
DOE OSTI2021

High-Rate Long Cycle-Life Li-Air Battery Aided by Bifunctional InX3 (X = I and Br) Redox Mediators

Redox mediators (RMs) are solution-based additives that have been extensively used to reduce the charge potential and increase the energy efficiency of Li–oxygen (Li–O 2 ) batteries. However, in the presence of RMs, achieving a long cycle-life operation of Li–O 2 batteries at a high current rate is still a major challenge. In this study, we discover a novel synergy among InX 3 (X = I and Br) bifunctional RMs, molybdenum disulfide (MoS 2 ) nanoflakes as the air electrode, dimethyl sulfoxide/ionic liquid hybrid electrolyte, and LiTFSI as a salt to achieve long cycle-life operations of Li–O 2 batteries in a dry air environment at high charge–discharge rates. Our results indicate that batteries with InI3 operate up to 450 cycles with a current density of 0.5 A g –1 and 217 cycles with a current density of 1 A g –1 at a fixed capacity of 1 A h g –1 . Batteries with InBr 3 operate up to 600 cycles with a current density of 1 A g –1 . These batteries can also operate at a higher charge rate of 2 A g –1 up to 200 cycles (for InBr 3 ) and 160 cycles (for InI 3 ). Our experimental and computational results reveal that while X 3 – is the source of the redox mediator, LiX at the MoS 2 cathode, In 3+ reacts on the lithium anode side to form a protective layer on the surface, thus acting as an effective bifunctional RM in a dry air environment. This evidence for a simultaneous improvement in the current rates and cycle life of a battery in a dry air atmosphere opens a new direction for research for advanced energy storage systems.

25 ENERGY STORAGE↗
DOE OSTI2022

Excitation Intensity- and Size-Dependent Halide Photosegregation in CsPb(I 0.5 Br 0.5 ) 3 Perovskite Nanocrystals

Although broad consensus exists that photoirradiation of mixed-halide lead perovskites leads to anion segregation, no model today fully rationalizes all aspects of this near ubiquitous phenomenon. In this work, we quantitatively compare experimental, CsPb(I 0.5 Br 0.5 ) 3 nanocrystal (NC) terminal anion photosegregation stoichiometries and excitation intensity thresholds to a band gap-based, thermodynamic model of mixed-halide perovskite photosegregation. Mixed-halide NCs offer strict tests of theory given physical sizes, which dictate local photogenerated carrier densities. We observe that mixed-anion perovskite NCs exhibit significant robustness to photosegregation, with photosegregation propensity decreasing with decreasing NC size. Observed size- and excitation intensity-dependent photosegregation data agree with model predicted size- and excitation intensity-dependent terminal halide stoichiometries. Established correspondence between experiment and theory, in turn, suggests that mixed-halide perovskite photostabilities can be predicted a priori using local gradients of (empirical) Vegard’s law expressions of composition-dependent band gaps.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Ag Intercalation in Layered Cs 3 Bi 2 Br 9 Perovskite for Enhanced Light Emission with Bound Interlayer Excitons

Cesium bismuth bromide (CBB) has garnered considerable attention as a vacancy-ordered layered perovskite with notable optoelectronic applications. However, its use as a light source has been limited due to its weak photoluminescence (PL). Here, we demonstrate metal intercalation as a novel approach to engineer the room-temperature PL of CBB using experimental and computational methods. Ag, when introduced into CBB, occupies vacant sites in the spacer region, forming octahedral coordination with surrounding Br anions. First-principles density functional theory calculations reveal that intercalated Ag represents the most energetically stable Ag species compared to other potential forms, such as Ag substituting Bi. The intercalated Ag forms a strong polaronic trap state close to the conduction band minimum and quickly captures photoexcited electrons with holes remaining in CBB layers, leading to the formation of a bound interlayer exciton, or BIE. The radiative recombination of this BIE exhibits bright room-temperature PL at 600 nm and a decay time of 38.6 ns, 35 times greater than that of free excitons, originating from the spatial separation of photocarriers by half a unit cell separation distance. The BIE as a new form of interlayer exciton is expected to inspire new research directions for vacancy-ordered perovskites.

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

Ferromagnetism out of charge fluctuation of strongly correlated electrons in κ -(BEDT-TTF) 2 Hg(SCN) 2 Br

We perform magnetic susceptibility and magnetic torque measurements on the organic κ-(BEDT-TTF) 2 Hg(SCN) 2 Br, which is recently suggested to host an exotic quantum dipole-liquid in its low-temperature insulating phase. Below the metal-insulator (MI) transition temperature, the magnetic susceptibility follows a Curie–Weiss law with a positive Curie–Weiss temperature, and a particular M∝ $\sqrt{H}$ curve is observed. The emergent ferromagnetically interacting spins amount to about 1/6 of the full spin moment of localized charges. Taking account of the possible inhomogeneous quasi-charge-order that forms a dipole-liquid, we construct a model of antiferromagnetically interacting spin chains in two adjacent charge-ordered domains, which are coupled via fluctuating charges on a Mott-dimer at the boundary. We find that the charge fluctuations can draw a weak ferromagnetic moment out of the spin singlet domains.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Quantum mechanical dataset of 836k neutral closed-shell molecules with up to 5 heavy atoms from C, N, O, F, Si, P, S, Cl, Br

Abstract We introduce the Vector-QM24 (VQM24) dataset comprehensively covering all possible neutral closed-shell small organic and inorganic molecules with up to five heavy (p-block) atoms: C, N, O, F, Si, P, S, Cl, Br. All valid stoichiometries, Lewis-rule-consistent graphs, and stable conformers (identified via GFN2-xTB) were enumerated combinatorially, yielding 577k conformational isomers spanning 258k constitutional isomers and 5,599 unique stoichiometries. DFT (ωB97X-D3/cc-pVDZ) optimizations were performed for all, and diffusion quantum Monte Carlo (DMC@PBE0(ccECP/cc-pVQZ)) energies are provided for 10,793 lowest-energy conformers with up to 4 heavy atoms. VQM24 includes structures, vibrational modes, rotational constants, thermodynamic properties (Gibbs free energies, enthalpies, ZPVEs, entropies, heat capacities), and electronic properties such as atomization, electron interaction, exchange-correlation, dispersion energies, multipole moments (dipole to hexadecapole), alchemical potentials, Mulliken charges, and wavefunctions. Machine learning models of atomization energies on this dataset reveal significantly higher complexity than QM9, with none achieving chemical accuracy. VQM24 offers a rigorous, high-fidelity benchmark for evaluating quantum machine learning models.

Science & Technology - Other Topics↗
DOE OSTI2020

Properties of gaseous closo -[B 6 X 6 ] 2− dianions (X = Cl, Br, I)

The electronic properties, fragmentation by collision-induced dissociation and bond properties of gaseous closo -[B 6 X 6 ] 2− (X = Cl, Br, I) dianions are discussed and compared to their larger-sized [B 12 X 12 ] 2− analogues.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗