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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 793 records · Page 44
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Solvation Environment and Interface Dynamics of Li 2 B 12 H 12 and Li 2 B 12 F 12 Electrolytes Uncovered by Theory and Operando Optical and FTIR Spectroelectrochemistry

In this work, we evaluated two closo-borate salts (Li 2 B 12 H 12 and Li 2 B 12 F 12 ) in propylene carbonate from theoretical and experimental perspectives to understand how the coordination environment influences their spectroscopic and electrochemical properties. The coordination environments of the closo-borate salts were modeled via density functional theory (DFT) and molecular dynamics (MD). Vibrational spectra calculated from the predicted coordination environments are in agreement with experimentally measured steady-state FTIR data. This theoretical investigation also suggested that Li 2 B 12 F 12 would possess a higher ionic conductivity than Li 2 B 12 H 12 , which was corroborated experimentally. Additionally, an electrochemical cell was designed and fabricated that enabled operando optical and FTIR spectroelectrochemical (OP-IR-SEC) measurements. This allowed for the simultaneous measurement of the relative changes of species at a lithium electrode-liquid electrolyte interface and the visualization of lithium plating at the electrode surface. This technique could provide new chemical insights and potentially link optical changes at the electrode–electrolyte interface to specific chemical species in similar electrochemical systems. The Li 2 B 12 F 12 electrolyte was found to have a higher thermal stability, which may find utility in applications for batteries that are subject to high-temperature conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Probing the Active Sites of MoS 2 Based Hydrotreating Catalysts Using Modulation Excitation Spectroscopy

The reactive surface sites of MoS 2 hydrotreating catalysts (unpromoted as well as Co- and Ni-promoted) supported on MgAl 2 O 4 spinel were investigated with respect to the substitution of sulfur by oxygen using in situ XAS coupled with modulation excitation spectroscopy (MES). Specifically, MES experiments were carried out by periodically cycling between a H 2 O and H 2 S containing hydrogen gas mixture at 400 °C. Due to the low fraction of S–O exchange, conventional XANES and EXAFS data hardly showed any changes when these catalysts were exposed to increasing ratios of H 2 O to H 2 S in an H 2 atmosphere. XANES and EXAFS data extracted at the Mo K-edge by MES analysis showed that for approximately 1% of the Mo atoms, sulfur atoms are replaced by oxygen atoms when exposed to H 2 O, causing partial oxidation of these active sites. The reaction is reversible and Mo returns to its initial sulfide phase when H 2 O is removed and H 2 S is supplied in the feed. In the case of Co- and Ni-promoted catalysts, the magnitude of S–O exchange was found to be reduced, indicating the beneficial effect of promotion. MES at the Ni K-edge showed that Ni was oxidized during H 2 O exposure, which in turn delayed the Mo oxidation in the Ni-promoted catalyst. The structures of these catalysts under S–O exchange were modeled using density functional theory (DFT) calculations, showing that the edge atoms are affected strongly. For all three catalysts, OH substitution is more favorable, while O substitution could be possible at high H 2 O pressure for unpromoted MoS 2 . Mo K-edge XANES spectra calculated using these simulated structures support the results obtained from the MES experiments. In conclusion, the presented approach using MES in combination with XAS and supported by DFT can be extended in general to catalysts under operando conditions and is thus a useful tool for determination of the active site on an atomic-scale.

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

Charge Disproportionation at Twisted SrTiO 3 Bilayer Interface Driven by Local Atomic Registry

The interplay of lattice, orbital, and charge degrees of freedom in complex oxide materials has hosted a plethora of exotic quantum phases and physical properties. Recent advances in the synthesis of freestanding complex oxide membranes and twisted heterostructures assembled from membranes provide diverse opportunities for discovery using moiré design with local lattice control. To this end, we designed moiré crystals at the coincidence site lattice condition, providing commensurate structure within the moiré supercell arising from the multiatom complex oxide unit cell. We fabricated such twisted bilayers from freestanding SrTiO 3 membranes and used depth-sectioning-based electron microscopic methods to investigate ordered charge states at the moiré interface. By selectively imaging SrTiO 3 atomic planes at different depths through the bilayer, we clearly resolved the moiré periodic structure at the twisted interface and found that it exhibits lattice-dependent charge disproportionation in the local atomic registry within the moiré supercell. Density functional modeling of the twisted oxide interface predicts that these moiré phenomena are accompanied by a two-dimensional flat band that can drive exceptional electronic phases. Our work provides a robust strategy for controlling moiré periodicity in twisted oxides and paves pathways to exploit the extraordinary functionalities via moiré lattice-driven charge-orbital correlation.

charge disproportionation↗
DOE OSTI2020

Enhancement of van der Waals Interlayer Coupling through Polar Janus MoSSe

Interlayer coupling plays essential roles in the quantum transport, polaritonic, and electrochemical properties of stacked van der Waals (vdW) materials. In this work, we report the unconventional interlayer coupling in vdW heterostructures (HSs) by utilizing an emerging 2D material, Janus transition metal dichalcogenides (TMDs). In contrast to conventional TMDs, monolayer Janus TMDs have two different chalcogen layers sandwiching the transition metal and thus exhibit broken mirror symmetry and an intrinsic vertical dipole moment. Such a broken symmetry is found to strongly enhance the vdW interlayer coupling by as much as 13.2% when forming MoSSe/MoS 2 HS as compared to the pristine MoS 2 counterparts. Our noncontact ultralow-frequency Raman probe, linear chain model, and density functional theory calculations confirm the enhancement and reveal the origins as charge redistribution in Janus MoSSe and reduced interlayer distance. Furthermore, our results uncover the potential of tuning interlayer coupling strength through Janus heterostacking.

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

Efficient Intermolecular Charge Transport in π-Stacked Pyridinium Dimers Using Cucurbit[8]uril Supramolecular Complexes

Intermolecular charge transport through π-conjugated molecules plays an essential role in biochemical redox processes and energy storage applications. In this work, we observe highly efficient intermolecular charge transport upon dimerization of pyridinium molecules in the cavity of a synthetic host (cucurbit[8]uril, CB[8]). Stable, homoternary complexes are formed between pyridinium molecules and CB[8] with high binding affinity, resulting in an offset stacked geometry of two pyridiniums inside the host cavity. The charge transport properties of free and dimerized pyridiniums are characterized using a scanning tunneling microscope-break junction (STM-BJ) technique. Our results show that π-stacked pyridinium dimers exhibit comparable molecular conductance to isolated, single pyridinium molecules, despite a longer transport pathway and a switch from intra- to intermolecular charge transport. Control experiments using a CB[8] homologue (cucurbit[7]uril, CB[7]) show that the synthetic host primarily serves to facilitate dimer formation and plays a minimal role on molecular conductance. Molecular modeling using density functional theory (DFT) reveals that pyridinium molecules are planarized upon dimerization inside the host cavity, which facilitates charge transport. In addition, the π-stacked pyridinium dimers possess large intermolecular LUMO–LUMO couplings, leading to enhanced intermolecular charge transport. Altogether, this work demonstrates that supramolecular assembly can be used to control intermolecular charge transport in π-stacked molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Emergence of multiple fluorophores in individual cesium lead bromide nanocrystals

Abstract Cesium-based perovskite nanocrystals (PNCs) possess alluring optical and electronic properties via compositional and structural versatility, tunable bandgap, high photoluminescence quantum yield and facile chemical synthesis. Despite the recent progress, origins of the photoluminescence emission in various types of PNCs remains unclear. Here, we study the photon emission from individual three-dimensional and zero-dimensional cesium lead bromide PNCs. Using photon antibunching and lifetime measurements, we demonstrate that emission statistics of both type of PNCs are akin to individual molecular fluorophores, rather than traditional semiconductor quantum dots. Aided by density functional modelling, we provide compelling evidence that green emission in zero-dimensional PNCs stems from exciton recombination at bromide vacancy centres within lead-halide octahedra, unrelated to external confinement. These findings provide key information about the nature of defect formation and the origin of emission in cesium lead halide perovskite materials, which foster their utilization in the emerging optoelectronic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Emergent geometry and duality in the carbon nucleus

Abstract The carbon atom provides the backbone for the complex organic chemistry composing the building blocks of life. The physics of the carbon nucleus in its predominant isotope, 12 C, is similarly full of multifaceted complexity. Here we provide a model-independent density map of the geometry of the nuclear states of 12 C using the ab initio framework of nuclear lattice effective field theory. We find that the well-known but enigmatic Hoyle state is composed of a “bent-arm” or obtuse triangular arrangement of alpha clusters. We identify all of the low-lying nuclear states of 12 C as having an intrinsic shape composed of three alpha clusters forming either an equilateral triangle or an obtuse triangle. The states with the equilateral triangle formation also have a dual description in terms of particle-hole excitations in the mean-field picture.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2019

Reply to: Reconsidering X-ray plasmons

In this response we show a spectral and X-ray intensity analysis that unequivocally proves a spectrally resolved plasmon reported in ref. 1. The analysis takes the f-sum rules into account, is consistent with the independently and simultaneously measured wavenumber-resolved X-ray scattering signal and compares well with advanced elastic feature modelling, including density functional theory for molecular dynamics (DFTMD) as well as pseudoatom molecular dynamics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance

Ultrafast time-resolved studies of photocatalytic thin films can provide a wealth of information crucial for understanding and thereby improving the performance of these materials by directly probing electronic structure, reaction intermediates, and charge carrier dynamics. The interpretation of transient spectra, however, can be complicated by thermally induced structural distortions, which appear within the first few picoseconds following excitation due to carrier–phonon scattering. Here we present a comparison of ex situ steady-state thermal difference spectra and transient absorption spectra spanning from NIR to hard X-ray energies of hematite thin films grown by atomic layer deposition. We find that beyond the first 100 picoseconds, the transient spectra measured for all excitation wavelengths and probe energies are almost entirely due to thermal effects as the lattice expands in response to the ultrafast temperature jump and then cools to room temperature on the microsecond timescale. At earlier times, a broad excited state absorption band that is assigned to free carriers appears at 675 nm, and the lifetime and shape of this feature also appear to be mostly independent of excitation wavelength. The combined spectroscopic data, which are modeled with density functional theory and full multiple scattering calculations, support an assignment of the optical absorption spectrum of hematite that involves two LMCT bands that nearly span the visible spectrum. Lastly, our results also suggest a framework for shifting the ligand-to-metal charge transfer absorption bands of ferric oxide films from the near-UV further into the visible part of the solar spectrum to improve solar conversion efficiency.

14 SOLAR ENERGY↗
DOE OSTI2023

Interaction energy and isosteric heat of adsorption between hydrogen and magnesium diboride

Hydrogen storage materials form a crucial research topic for future energy utilization employing hydrogen and among those of interest magnesium diboride (MgB 2 ) has shown its prevalence. In this study, a first-principles analytical adsorption model of one hydrogen molecule in the vicinity of various magnesium diboride crystal surfaces was developed in order to obtain surface thermodynamic properties as a function of molecular and lattice properties. Henry's law constant (K H ) and isosteric heat of adsorption (ΔH ads ) indicators of the affinity between a gaseous molecule and a solid surface are thus calculated. The results in this paper not only address questions pertaining to the first stage of hydrogen storage processes but also advance the understanding of physisorption thermodynamics of a neutral molecule (H 2 ) coming in contact with a layered metallic-like surface (MgB 2 ). Although the model is built from a framework of classical calculations, quantum effects are incorporated as the fractional charge of the ions on the free surfaces, which is essential for the calculation of analytic thermodynamic values that approximate calculations from other methods. To benchmark our theoretical models, periodic density functional calculations were performed to determine the interactions between H 2 and different MgB 2 surfaces from first-principles. By considering both the top and sublayers of MgB 2 in calculating interaction energy, we have analytically and computationally calculated the interaction energies of H 2 molecules and MgB 2 's terminated planes, and witnessed the strong dependence of interaction energies on surface charges. We have also observed a dipole flipping phenomenon which explains the discontinuity seen in the interaction energy graph of Mg(0001). Both analytical and computational results showed heat of adsorption at zero coverage varying at a very low range (<7 kJ mol -1 ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Continuum kinetic and multi-fluid simulations of classical sheaths

The kinetic study of plasma sheaths is critical, among other things, to understand the deposition of heat on walls, the effect of sputtering, and contamination of the plasma with detrimental impurities. The plasma sheath also provides a boundary condition and can often have a significant global impact on the bulk plasma. In this paper, kinetic studies of classical sheaths are performed with the continuum kinetic code, Gkeyll, which directly solves the Vlasov-Maxwell equations. The code uses a novel version of the finite-element discontinuous Galerkin scheme that conserves energy in the continuous-time limit. The fields are computed using Maxwell equations. Ionization and scattering collisions are included; however, surface effects are neglected. The aim of this work is to introduce the continuum kinetic method and compare its results with those obtained from an already established finite-volume multi-fluid model also implemented in Gkeyll. Novel boundary conditions on the fluids allow the sheath to form without specifying wall fluxes, so the fluids and fields adjust self-consistently at the wall. Our work demonstrates that the kinetic and fluid results are in agreement for the momentum flux, showing that in certain regimes, a multifluid model can be a useful approximation for simulating the plasma boundary. There are differences in the electrostatic potential between the fluid and kinetic results. Further, the direct solutions of the distribution function presented here highlight the non-Maxwellian distribution of electrons in the sheath, emphasizing the need for a kinetic model. The densities, velocities, and the potential show a good agreement between the kinetic and fluid results. But, kinetic physics is highlighted through higher moments such as parallel and perpendicular temperatures which provide significant differences from the fluid results in which the temperature is assumed to be isotropic. Besides decompression cooling, the heat flux is shown to play a role in the temperature differences that are observed, especially inside the collisionless sheath. Published by AIP Publishing.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2018

Soft X-ray backlighter source driven by a short-pulse laser for pump-probe characterization of warm dense matter

In this paper, we propose a pump-probe X-ray absorption spectroscopy temperature measurement technique appropriate for matter having temperature in the range of 10 to a few 100 eV and density up to solid density. Atomic modeling simulations indicate that for various low- to mid-Z materials in this range the energy and optical depth of bound-bound and bound-free absorption features are sensitive to temperature. We discuss sample thickness and tamp layer considerations. A series of experimental investigations was carried out using a range of laser parameters with pulse duration ≤5 ps and various pure and alloyed materials to identify backlighter sources suitable for the technique.

47 OTHER INSTRUMENTATION↗
DOE OSTI2018

Implementation of a dislocation-density based single-crystal model into a continuum shock hydrodynamics code

The dynamic thermomechanical responses of polycrystalline materials under shock loading are often dominated by the interaction of defects and interfaces. For example, within metals, a prescribed deformation associated with a shock wave may be accommodated by crystallographic slip, provided a sufficient population of mobile dislocations is available. However, if the deformation rate is large enough, there may be an insufficient number of freely mobile dislocations. In this case, additional dislocations may be nucleated, or alternate mechanisms (e.g. twinning, damage) activated in order to accommodate the deformation. Furthermore, direct numerical simulation at the mesoscale offers insight into these physical processes that can be invaluable to the development of macroscale constitutive theories, if the mesoscale models adequately represent the anisotropic nonlinear thermomechanical response of individual crystals and their interfaces.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Experimental and theoretical study of hole scattering in RF sputtered p-type Cu 2 O thin films

One of the key materials of interest for p-type oxide semiconductor thin film electronics is cuprous oxide (Cu 2 O), due to its relatively high hole mobility. Here, in this work, we use experiments, analytical models, and density functional theory calculations to study the scattering mechanisms that determine Hall mobility in two Cu 2 O samples. First, we examine a polycrystalline Cu 2 O thin film deposited by RF magnetron sputtering, and second, a single-crystalline Cu2O bulk substrate. Temperature-dependent Hall measurements indicate that neutral impurity and grain boundary scattering are dominant for the polycrystalline Cu 2 O thin film, while phonon scattering is dominant for single-crystalline Cu 2 O. Our first-principles calculations show that the room-temperature intrinsic hole mobility of Cu 2 O is 106 cm 2 V –1 s –1 , indicating the great promise of the material for p-type electronic devices. This intrinsic mobility is limited by phonon scattering, with the most dominant scattering modes having phonon energies of 88.4 and 17.1 meV. These results indicate that the key pathways to increase the hole mobility in Cu 2 O thin films are by reducing the impurity concentration and by increasing grain size. Our work thus sets the stage for the future development of high performance Cu 2 O-based p-type thin film transistors.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Learning to predict the cosmological structure formation

Matter evolved under the influence of gravity from minuscule density fluctuations. Nonperturbative structure formed hierarchically over all scales and developed non-Gaussian features in the Universe, known as the cosmic web. To fully understand the structure formation of the Universe is one of the holy grails of modern astrophysics. Astrophysicists survey large volumes of the Universe and use a large ensemble of computer simulations to compare with the observed data to extract the full information of our own Universe. However, to evolve billions of particles over billions of years, even with the simplest physics, is a daunting task. We build a deep neural network, the Deep Density Displacement Model ( D 3 M ), which learns from a set of prerun numerical simulations, to predict the nonlinear large-scale structure of the Universe with the Zel’dovich Approximation (ZA), an analytical approximation based on perturbation theory, as the input. Our extensive analysis demonstrates that D 3 M outperforms the second-order perturbation theory (2LPT), the commonly used fast-approximate simulation method, in predicting cosmic structure in the nonlinear regime. We also show that D 3 M is able to accurately extrapolate far beyond its training data and predict structure formation for significantly different cosmological parameters. Our study proves that deep learning is a practical and accurate alternative to approximate 3D simulations of the gravitational structure formation of the Universe.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2016

A cosmographic analysis of the transition to acceleration using SN-Ia and BAO

We explore the distance-redshift relation using a cosmographic methodology, and show how the cosmographic parameters can be used to determine the redshift of transition from deceleration to acceleration. Such a transition at a low redshift occupies only a small region of the available parameter space, and the prior assumption of an early period of deceleration can significantly change the posterior constraints. We use available type Ia Supernovae (SN-Ia) and Baryon Acoustic Oscillation (BAO) data sets to determine the cosmographic deceleration q {sub 0}, jerk j {sub 0}, snap s {sub 0} and lerk l {sub 0} parameters. The parameters are consistent with the ΛCDM model for a flat universe within 2-sigma. We derive constraints on the redshift of transition from deceleration to acceleration for the different expansions, and find z {sub acc} > 0.14 at 95% confidence in the most conservative case.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

More about a successful vector-tensor theory of gravitation

The vector-tensor (VT) theory of gravitation revisited in this article was studied in previous papers, where it was proved that VT works and deserves attention. New observational data and numerical codes have motivated further development which is presented here. New research has been planed with the essential aim of proving that current cosmological observations, including Planck data, baryon acoustic oscillations (BAO), and so on, may be explained with VT, a theory which accounts for a kind of dark energy which has the same equation of state as vacuum. New versions of the codes CAMB and COSMOMC have been designed for applications to VT, and the resulting versions have been used to get the cosmological parameters of the VT model at suitable confidence levels. The parameters to be estimated are the same as in general relativity (GR), plus a new parameter D . For D = 0, VT linear cosmological perturbations reduces to those of GR, but the VT background may explain dark energy. The fits between observations and VT predictions lead to non vanishing | D | upper limits at the 1σ confidence level. The value D = 0 is admissible at this level, but this value is not that of the best fit in any case. Results strongly suggest that VT may explain current observations, at least, as well as GR; with the advantage that, as it is proved in this paper, VT has an additional parameter which facilitates adjustments to current observational data.

79 ASTRONOMY AND ASTROPHYSICS↗