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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Self-Assembly of Anisotropic Particles on Curved Surfaces

The surface curvature of membranes, interfaces, and substrates plays a crucial role in shaping the self-assembly of particles adsorbed on these surfaces. However, little is known about the interplay between particle anisotropy and surface curvature and how they couple to alter the free energy landscape of particle assemblies. Using molecular dynamics simulations, we investigate the effect of prescribed curvatures on a quasi-2D assembly of anisotropic patchy particles. By varying curvature and surface coverage, we uncover a rich geometric phase diagram, with curvature inducing ordered structures entirely absent on planar surfaces. Large spatial domains of ordered structures can contain hidden microdomains of orientational textures imprinted by the surface on the assembly. The dynamical landscape is also reshaped by surface curvature, with a glass-like state emerging at modest densities and high curvature. Changes to the symmetry of the surface curvature are found to result in distinct structures, including phases with mesoscale ordering. In conclusion, our findings show that the coupling between surface curvature and particle geometry opens an unexplored space of morphologies and structures that can be exploited for material design.

Fluids↗
DOE OSTI2020

Iron telluride ladder compounds: Predicting the structural and magnetic properties of BaFe 2 Te 3

Since the discovery of pressure-induced superconductivity in the two-leg ladder system BaFe 2 X 3 (X=S, Se), with the 3d iron electronic density n=6, quasi-one-dimensional iron-based ladders have attracted considerable attention. In this work, we use density-functional theory to predict that the novel n=6 iron ladder BaFe 2 Se 3 could be stable with a similar crystal structure as BaFe 2 Se 3 . Furthermore, our results also indicate that BaFe2Te3 will display a complex 2×2 block-type magnetic order. Due to the magnetic striction effects of this block order, BaFe2Te3 should be a magnetic noncollinear ferrielectric system with a net polarization 0.31μC/cm2. In summary, the similar electronic density and magnetic ground state of Te- and Se-based ladders indicates both should display similar properties. In particular, the physical and structural similarity with BaFe 2 Se 3 suggests that BaFe 2 Se 3 could become superconducting under high pressure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

In Situ Formation of Li 3 P Layer Enables Fast Li + Conduction across Li/Solid Polymer Electrolyte Interface

Abstract Solid‐state polymer electrolytes provide better flexibility and electrode contact than their ceramic counterparts, making them a worthwhile pursuit for all‐solid‐state lithium‐metal batteries. However, their large Li/solid state electrolyte interfacial resistance, small critical current density, and rapid lithium dendrite growth during cycling still limit their viability. Owing to these restrictions, all‐solid‐state cells with solid polymer electrolytes must be cycled above room‐temperature and with a small current density. These problems can be mitigated with an in situ formed artificial solid electrolyte interphase that rapidly conducts Li + ions. Herein, a Li 3 P layer formed in situ at the Li‐metal/solid polymer electrolyte interphase is reported that significantly reduces the electrode/electrolyte interfacial resistance. Additionally, this layer increases the wettability of the solid polymer by the metallic lithium anode, allowing for the critical current density of lithium symmetric cells to be doubled by homogenizing the current density at the interface. All‐solid‐state Li/Li symmetric cells and Li/LiFePO 4 cells with the Li 3 P layer show improved cycling performance with a high current density.

Wu, Nan↗
DOE OSTI2021

Electronic structure of rhombohedral Cr X 3 ( X = Br, Cl, I) van der Waals crystals

We perform a comprehensive analysis of both the chemical and correlated electronic structure reconstruction of rhombohedral Cr X 3 (X = Br, Cl, I) van der Waals bulk crystals. Using the generalized gradient approximation (GGA) plus dynamical mean-field theory we explicitly demonstrate the importance of local dynamical correlations for a consistent understanding of emergent Kondo quasiparticles and Mott localized electronic states, showing the interplay between material-dependent one-electron GGA line-shape and multiorbital electronic interactions. To probe the correlated paramagnetic electronic state we performed x-ray absorption spectroscopy measurements for CrCl 3 and CrBr 3 bulk crystals. Furthermore, our correlated many-body study is relevant to understanding the electronic structure reconstruction of paramagnetic Cr-trihalide crystals and should be widely applicable to other van der Waals magnetic materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

The Maximal Entanglement Limit in Statistical and High-energy Physics

These lectures advocate the idea that quantum entanglement provides a unifying foundation for both statistical physics and high-energy interactions. I argue that, at sufficiently long times or high energies, most quantum systems approach a Maximal Entanglement Limit (MEL) in which phases of quantum states become unobservable, reduced density matrices acquire a thermal form, and probabilistic descriptions emerge without invoking ergodicity or classical randomness. Within this framework, the emergence of probabilistic parton model, thermalization in the break-up of confining strings and in high-energy collisions, and the universal small-x behavior of structure functions arise as direct consequences of entanglement and geometry of high-dimensional Hilbert space.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Interplay of structural fluctuations and charge carrier dynamics is key for high performance of hybrid lead halide perovskites

The ability of methylammonium lead triiodide (MAPbI 3 ) to achieve photoelectric conversion efficiency that is on par with crystalline silicon has led to a surge of interest in perovskite photovoltaics. However, an in-depth understanding of how the ubiquitous coupling between the fast rovibrational movements of the organic cations and the phonon vibrations of the inorganic framework affects the relaxation and recombination of hot carriers remains largely elusive. Access to such knowledge is critical to guide design and increase efficiency of new classes of perovskite solar cells. In this report, we report a time-domain ab initio investigation of temperature dependent excited state dynamics in MAPbI 3 , with particular emphasis on nuclear anharmonic effects. The observed strong anharmonicity is attributed to softness of the material and unusual dynamical coupling between the organic and inorganic components. At an elevated temperature, the hydrogen bonding between MA and iodines is weakened, enhancing rotation of MA cations, which become more dynamically disordered. As a result, thermal vibrations of the inorganic Pb–I sublattice are suppressed, and the lattice anharmonicity is decreased. Thermal fluctuations of the electronic energy levels are found to follow the trend of anharmonic motions of Pb and I atoms, with holes relaxing faster to the band edges than electrons, due to higher density of the hole states. While elevated temperature accelerates intraband carrier cooling, it slows nonradiative carrier recombination. The latter result is important for performance, since solar cells and other devices heat up during operation. The reported signatures of coupled structural dynamics of the organic cations and inorganic framework unravel the interplay between anomalous structural fluctuations and charge carrier dynamics, which is of particular importance for fundamental understanding of the structure–property relationships in hybrid metal halide perovskites.

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

Mott localization in the van der Waals crystal CrI 3 : A GGA+DMFT study

Using the generalized gradient approximation plus dynamical mean-field theory (GGA+DMFT) we confirm the importance of multi-orbital dynamical correlations in determining the paramagnetic insulating state of CrI 3 . Furthermore, while the ferromagnetic phase reveals weak electronic correlation effects due to strong spin-orbital polarization, the Mott insulating state of paramagnetic CrI 3 crystal is shown to be driven by the interplay between orbital-dependent one-electron lineshape and multi-orbital electronic interactions. To probe the paramagnetic Mott insulating state we performed x-ray absorption spectroscopy (XAS) measurements for the two structural phases of CrI 3 . Our study is relevant to understanding the orbital-selective electronic structure reconstruction of Mott insulators and should be applicable to other van der Waals bonded materials from bulk to the ultrathin limit.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Hole–hole Tamm–Dancoff-approximated density functional theory: A highly efficient electronic structure method incorporating dynamic and static correlation

The study of photochemical reaction dynamics requires accurate as well as computationally efficient electronic structure methods for the ground and excited states. While time-dependent density functional theory (TDDFT) is not able to capture static correlation, complete active space self-consistent field methods neglect much of the dynamic correlation. Hence, inexpensive methods that encompass both static and dynamic electron correlation effects are of high interest. Here, we revisit hole–hole Tamm–Dancoff approximated (hh-TDA) density functional theory for this purpose. The hh-TDA method is the hole–hole counterpart to the more established particle–particle TDA (pp-TDA) method, both of which are derived from the particle–particle random phase approximation (pp-RPA). In hh-TDA, the N-electron electronic states are obtained through double annihilations starting from a doubly anionic (N+2 electron) reference state. In this way, hh-TDA treats ground and excited states on equal footing, thus allowing for conical intersections to be correctly described. Furthermore, the treatment of dynamic correlation is introduced through the use of commonly employed density functional approximations to the exchange-correlation potential. Additionally, we show that hh-TDA is a promising candidate to efficiently treat the photochemistry of organic and biochemical systems that involve several low-lying excited states—particularly those with both low-lying ππ* and nπ* states where inclusion of dynamic correlation is essential to describe the relative energetics. In contrast to the existing literature on pp-TDA and pp-RPA, we employ a functional-dependent choice for the response kernel in pp- and hh-TDA, which closely resembles the response kernels occurring in linear response and collinear spin-flip TDDFT.

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

Advanced Fabrication Techniques of Metal Hydrides for Science and Technology Applications (Abbreviated Final Report)

Lithium Hydride (LiH) atomic properties make it an excellent candidate for thermal energy storage, hydrogen storage, and nuclear reactor technology. High Energy Density (HED) experiments on LiH at the National Ignition Facility (NIF) can also provide critical Equation of State (EOS) and Hugoniot data. Density requirements for LiH vary per application and therefore physical and structural requirements for LiH are non-uniform. Historical production of LiH relies on casting processesthat are limited by density and grain-size control, which leads to unfavorable machinable characteristics. LiH manufacturing is further hindered due to its chemical reactivity and propensity to readily react with moisture. This work aimed at exploring advanced fabrication techniques for LiH such as 1) uniaxial powder pressing methods and 2) laser powder bed fusion (L-PBF) additive manufacturing. Uniaxial powder compaction offers advantageous tailorable mechanical and physical properties via density control, and L-PBF can produce net-shaped complex parts with unique microstructure. Uniaxial pressing proved successful in readily producing LiH with density control.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Advanced Fabrication Techniques of Metal Hydrides for Science and Technology Applications (Full Technical Report)

Lithium Hydride (LiH) atomic properties make it an excellent candidate for thermal energy storage, hydrogen storage, and nuclear reactor technology. High Energy Density (HED) experiments on LiH at the National Ignition Facility (NIF) can also provide critical Equation of State (EOS) and Hugoniot data. Density requirements for LiH vary per application and therefore physical and structural requirements for LiH are non-uniform. Historical production of LiH relies on casting processes that are limited by density and grain-size control, which leads to unfavorable machinable characteristics. LiH manufacturing is further hindered due to its chemical reactivity and propensity to readily react with moisture. This work aimed at exploring advanced fabrication techniques for LiH such as 1) uniaxial powder pressing methods and 2) laser powder bed fusion (L-PBF) additive manufacturing. Uniaxial powder compaction offers advantageous tailorable mechanical and physical properties via density control, and L-PBF can produce net-shaped complex parts with unique microstructure. Uniaxial pressing proved successful in readily producing LiH with density control.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Selective bond formation triggered by short optical pulses: quantum dynamics of a four-center ring closure

Here we report bond formation induced by an ultrashort UV pulse. The photochemical process is described by quantum dynamics as coherent electronic and nuclear motions during the ultrashort pulse induced ring closure of norbornadiene to quadricyclane. Norbornadiene consists of two ethylene moieties connected by a rigid (CH 2 ) 3 bridge. Upon photoexcitation, two new sigma bonds are formed, resulting in the closure of a four-atom ring. As a medium-sized polyatomic molecule, norbornadiene exhibits a high density of strongly coupled electronic states from about 6 eV above the ground state. We report on inducing the formation of the new bonds using a short femtosecond UV pulse to pump a non-equilibrium electronic density in the open form that evolves towards the closed ring form. As the coherent electronic-nuclear coupled dynamics unfold, the excited states change character through non-adiabatic interactions and become valence states for the two new C–C bonds of quadricyclane. Our three-dimensional fully quantum dynamical grid simulations during the first 200 fs show that short UV pulses of different polarization initiate markedly different initial non-equilibrium electronic densities that follow different dynamical paths to the S 0 /S 1 conical intersection. They lead to different initial relative yields of quadricyclane, thereby opening the way to controlling bond-making with attopulses.

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

A Perturbative Solution for Nonlinear Stratified Upwelling over a Frictional Slope

Abstract A perturbative solution of simplified primitive equations for nonlinear weakly stratified upwelling over a frictional slope is found that resolves the vertical structure of velocity fields and can satisfy Ertel’s potential vorticity conservation in the stratified inviscid interior. The solution uses assumptions consistent with the model proposed by Lentz and Chapman, including a steady-state, constant cross-shore density gradient, no alongshore gradients, laterally inviscid, and consideration of cross-shore advection of alongshore momentum. The solution resolves the vertical structure of velocity fields (including subsurface maxima of compensational flow, not resolved by Lentz and Chapman) and can satisfy Ertel’s potential vorticity conservation in the stratified inviscid interior. The dynamics are similar to Lentz and Chapman; bottom stress balances alongshore wind stress in a homogeneous density ocean and is replaced by nonlinear cross-shore transport of alongshore momentum as the Burger number (S=αN/f, whereα,N, andfare the bottom slope, buoyancy frequency, Coriolis frequency, respectively) increases. When the solution uses the empirical relation between cross-shore and vertical density gradients proposed by Lentz and Chapman, vorticity conservation is not satisfied and the nonlinear momentum transport estimated by the solution linearly increases withS, asymptotically matching Lentz and Chapman forS< 1. When the solution conserves interior potential vorticity, the momentum transport is proportional toS 2 forS< 1 and is in better agreement with numerical simulations.

Oceanography↗
DOE OSTI2021

Electronic nature of chiral charge order in the kagome superconductor CsV 3 Sb 5

Kagome superconductors with T C up to 7 K have been discovered for over 40 y. Recently, unconventional chiral charge order has been reported in kagome superconductor KV 3 Sb 5 , with an ordering temperature of one order of magnitude higher than the T C . However, the chirality of the charge order has not been reported in the cousin kagome superconductor CsV 3 Sb 5 , and the electronic nature of the chirality remains elusive. In this paper, we report the observation of electronic chiral charge order in CsV 3 Sb 5 via scanning tunneling microscopy (STM). We observe a 2 × 2 charge modulation and a 1 × 4 superlattice in both topographic data and tunneling spectroscopy. 2 × 2 charge modulation is highly anticipated as a charge order by fundamental kagome lattice models at van Hove filling, and is shown to exhibit intrinsic chirality. We find that the 1 × 4 superlattices form various small domain walls, and can be a surface effect as supported by our first-principles calculations. Crucially, we find that the amplitude of the energy gap opened by the charge order exhibits real-space modulations, and features 2 × 2 wave vectors with chirality, highlighting the electronic nature of the chiral charge order. STM study at 0.4 K reveals a superconducting energy gap with a gap size 2Δ = 0.85 meV, which estimates a moderate superconductivity coupling strength with 2Δ/k B T C = 3.9. Furthermore, when further applying a c-axis magnetic field, vortex core bound states are observed within this gap, indicative of clean-limit superconductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Calculating adsorption isotherms using the two-phase thermodynamic method and molecular dynamics simulations

We describe the calculation of adsorption isotherms from molecular dynamics simulations based on the two-phase thermodynamic (2PT) model. The 2PT model developed for bulk fluid phases treats the gas-like components as hard spheres (HSs), which correctly recovers the limiting behaviors of unconfined fluids. We showed that this treatment, however, does not always lead to the correct zero-loading behavior in strongly confining systems. For methane adsorption into zeolite MFI, the HS reference state underestimates entropy by up to 20% at low loadings and leads to an order-of-magnitude increase in the adsorption onset pressure. To fix these issues, we propose the use of ideal adsorbed gas (IAG) as the gas reference model, the properties of which can be computed using the Widom insertion method on an empty adsorbent. We further describe three routes to compute adsorption isotherms from the Helmholtz free energy at different loadings. Comparing against established Monte Carlo (MC) methods, we found that the adsorption isotherms obtained using the IAG reference state agrees to within 40%, which corresponds to deviations of <5% in adsorption free energy. The isotherms calculated using the HS reference state underestimate the adsorption uptake at low to medium loadings in strongly confining systems, but its accuracy improves at higher loadings and as the pore size increases relative to the sorbate diameter. The methods described here provide an alternative approach for computing adsorption isotherms when MC simulations in an open ensemble are undesirable and enable a direct comparison of computed adsorption thermodynamics with experiments.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Equation of State of TiN at High Pressures and Temperatures: A Possible Host for Nitrogen in Planetary Mantles

Nitrogen, the most abundant element in Earth's atmosphere, is also a primary component of solid nitride minerals found in meteorites and on Earth's surface. If they remain stable to high pressures and temperatures, these nitrides may also be important reservoirs of nitrogen in planetary interiors. We used synchrotron X-ray diffraction to measure the thermal equation of state and phase stability of titanium nitride (TiN) in a laser-heated diamond anvil cell at pressures up to ~70 GPa and temperatures up to ~2500 K. TiN maintains the cubic B1 (NaCl-type) crystal structure over the entire pressure and temperature range explored. It has K 0 = 274(4) GPa, K 0 ' = 3.9(2), and γ 0 = 1.39(4) for a fixed V 0 = 76.516(30) Å 3 (based on experimental measurements), q = 1, and θ 0 = 579 K. Additionally, we collected Raman spectra of TiN up to ~60 GPa, where we find that the transverse acoustic (TA), longitudinal acoustic (LA), and transverse optical (TO) phonon modes exhibit mode Grüneisen parameters of 1.66(17), 0.54(15), and 0.93(4), respectively. Based on our equation of state, TiN has a density of ~5.6–6.4 g/cm 3 at Earth's lower mantle conditions, significantly more dense than both the mantle of the Earth and the estimated densities of the mantles of other terrestrial planets, but less dense than planetary cores. Furthermore, we find that TiN remains stable against physical decomposition at the pressures and temperatures found within Earth's mantle, making it a plausible reservoir for deep planetary nitrogen if chemical conditions allow its formation.

58 GEOSCIENCES↗
DOE OSTI2023

Time-Resolved Radioluminescence of the Polynuclear Copper(I) Phosphor Cu4I6²–. Different Temporal responses to Photo, X-Ray, β-Ray and α-Particle Excitation

Described for the first time are the time-resolved radioluminescence (TRRL) properties of the highly luminescent copper(I) cluster Cu4I62– using X-ray, b-ray and a-particle excitation. The copper(I) phosphors are two crystalline salts of this anion, [Na2(18-crown-6)2(H2O)3][Cu4I6] (I) and [Li(benzo-15-crown-5)2(H2O)]2[Cu4I6] (II), that had been shown to display strong photoluminescence (PL) when excited with ultraviolet light. The integrated radioluminescence (RL) spectra observed when pulsed X-rays were used as the excitation source are virtually the same as the PL spectra under comparable conditions. These temporal RL spectra are invariant at all observation times indicating that the observed scintillation occurs from a common excited state (or set of excited states). When the TRRL is collected from excitation with a pulsed X-ray source, b-ray decay from 90Sr or a-decay from 244Cm, the longer components (>2 μs) of the TRRL displayed (in each case) lifetimes comparable to those of the strictly exponential PL decays recorded under pulsed laser UV excitation. However, at shorter observation times (< 500 ns), the RL decay deviated from the exponential model, indicating a markedly different temporal luminescence behavior when these materials were excited with pulsed high energy radiation. Furthermore, this effect was the most pronounced for the a-particle excitation. These results suggest that the absorption of a very high energy X-ray photon, b-ray or a-particle at a site within the crystalline solid leads to a high local density of electronic excited states and that coupling between these states provides an alternative channel for excited state decay. Given that the patterns observed

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Electrochemistry at Back-Gated, Ultrathin ZnO Electrodes: Field-Effect Modulation of Heterogeneous Electron Transfer Rate Constants by 30× with Enhanced Gate Capacitance

We report steady-state voltammetry of outer-sphere redox species at back-gated ultrathin ZnO working electrodes in order to determine electron transfer rate constants k ET as a function of independently-controlled gate bias, V G . We demonstrate that k ET can be modulated as much as 30-fold by application of V G ≤ 8 V. Key to this demonstration was integrating the ultrathin (5 nm) ZnO on a high dielectric constant (k) insulator, HfO 2 (30 nm), which was grown on a Pd metal gate. The high-k HfO 2 dramatically decreased the required V G values and increased the gate-induced charge in ZnO compared to previous studies. Importantly, the enhanced gating power of the Pd/HfO 2 /ZnO stack meant it was possible to observe a non-monotonic dependence of k ET on V G , which reflects the inherent density of redox acceptor states in solution. Furthermore, this work adds to the growing body of literature demonstrating that electrochemical kinetics (i.e., rate constants and overpotentials) at ultrathin working electrodes can be tuned by V G , independent of the conventional electrochemical working electrode potential.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Multifunction Hydrophobic Ligand Engineered Cd(S, Se)/ZnS Quantum Dots for Stabilizing Highly Efficient Carbon‐Based Perovskite Solar Cells

The long-term operational stability of perovskite solar cells (PSCs) remains a key challenge impeding their commercialization, particularly due to ambient environments (e.g., moisture, oxygen, heat)-induced degradation. Carbon electrode-based PSCs have emerged as cost-effective and relatively stable alternatives to metal electrode-based devices due to carbon materials' hydrophobic behavior, yet they still lag in both long-term durability and power conversion efficiency (PCE). In this work, an ultrathin hydrophobic ligand-modified core–shell Cd(S,Se)/ZnS quantum dots (QDs) capping layer is introduced as a multifunctional interfacial modifier for carbon-electrode-based PSCs. This oleic acid ligand-modified QDs capping layer exhibits inherent hydrophobicity, effectively serving as a moisture barrier to retard perovskite degradation under ambient conditions. Furthermore, the strong interfacial bonding between the QDs and perovskite halide surfaces leads to efficient trap state passivation, reducing trap density and creating a more uniform electrical contact. The modified QDs/perovskite interface also features an elevated conduction band edge, promoting improved charge extraction. As a result, devices incorporating this quantum dot capping layer retain 98% of their initial PCE after 450 h of ambient aging and achieve a champion efficiency of 20.74%. As a result, this strategy highlights the potential of hydrophobic ligand-modified chalcogenide QDs as surface modifiers to enhance both the stability and performance of carbon-based PSCs, offering a promising route toward scalable fabrication of durable perovskite solar modules.

14 SOLAR ENERGY↗