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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 1,027 records · Page 57
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

A One-Dimensional Organic Lead Chloride Hybrid with Excitation-Dependent Broadband Emissions

Organic–inorganic metal halide hybrids have emerged as a new class of materials with fascinating optical and electronic properties. The exceptional structure tunability has enabled the development of materials with various dimensionalities at the molecular level, from three-dimensional (3D) to 2D, 1D, and 0D. Here, we report a new 1D lead chloride hybrid, C 4 N 2 H 14 PbCl 4 , which exhibits unusual inverse excitation-dependent broadband emission from bluish-green to yellow. Density functional theory calculations were performed to better understand the mechanism of this excitation-dependent broadband emission. This 1D hybrid material is found to have two emission centers, corresponding to the self-trapped excitons (STEs) and vacancy-bound excitons. The excitation-dependent emission is due to different populations of these two types of excitons generated at different excitation wavelengths. Furthermore, this work shows the rich chemistry and physics of organic–inorganic metal halide hybrids and paves the way to achieving novel light emitters with excitation-dependent broadband emissions at room temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Crystallizing Atomic Xenon in a Flexible MOF to Probe and Understand Its Temperature-Dependent Breathing Behavior and Unusual Gas Adsorption Phenomenon

Flexible metal–organic frameworks (MOFs) hold great promise as smart materials for specific applications such as gas separation. These materials undergo interesting structural changes in response to guest molecules, which is often associated with unique adsorption behavior not possible for rigid MOFs. Understanding the dynamic behavior of flexible MOFs is crucial yet challenging as it involves weak host–guest interactions and subtle structural transformation not only at the atomic/molecular level but also in a nonsteady state. Here we report an in-depth study on the adsorbate- and temperature-dependent adsorption in a flexible MOF by crystallizing atomic gases into its pores. Mn(ina)2 shows an interesting temperature-dependent response toward noble gases. Its nonmonotonic, temperature-dependent adsorption profile results in an uptake maximum at a temperature threshold, a phenomenon that is unusual. Full characterization of Xe-loaded MOF structures is performed by in situ single-crystal and synchrotron X-ray diffraction, IR spectroscopy, and molecular modeling. The X-ray diffraction analysis offers a detailed explanation into the dynamic structural transformation and provides a convincing rationalization of the unique adsorption behavior at the molecular scale. The guest and temperature dependence of the structural breathing gives rise to an intriguing reverse of Xe/Kr adsorption selectivity as a function of temperature. The presented work may provide further understanding of the adsorption behavior of noble gases in flexible MOF structures.

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

Size-Dependent Optical Band Gaps in Metal–Organic Framework Nanoparticles

Decades of research into size-dependent semiconductor optical gaps have focused on quantum confinement as the dominant mechanism. Emerging reports indicate that lattice strain─intentional or incidental─can impart optical shifts similar or greater in magnitude. Here, we report evidence of optical absorption and photoluminescence spectra of M(1,2,3-triazolate)2 (M = Mg, Cr, Mn, Fe, Co, Cu, Zn, or Cd) nanoparticles that blueshift from bulk values with decreasing particle sizes in a manner that defies explanation by conventional quantum confinement. Here, the phenomenon persists for particle sizes as large as 200 nm, whereas quantum confinement generally ceases beyond 20–30 nm diameters and follows a weaker dependence on the particle radius. Computational simulations and crystallographic analysis suggest that this behavior arises from size-dependent changes to metal–linker bonding that manifest in strain values comparable to literature reports of strain-induced optical shifts in other classes of materials. This behavior appears beyond this family of materials in other notable examples of metal–organic frameworks (MOFs), including the well-studied Cu3(trimesate)2 (CuBTC), where smaller sizes correlate with blueshifted optical gaps. Taken together, these results represent one of the few examples of size-dependent strain in crystalline materials and reinforce the emerging view that MOFs become softer materials when isolated as nanoparticles.

Electrical conductivity↗
DOE OSTI2011

On the propagation of a quasi-static disturbance in a heterogeneous, deformable, and porous medium with pressure-dependent properties

Using an asymptotic technique, valid when the medium properties are smoothly-varying, I derive a semi-analytic expression for the propagation velocity of a quasi-static disturbance traveling within a nonlinear-elastic porous medium. The phase, a function related to the propagation time, depends upon the properties of the medium, including the pressure-sensitivities of the medium parameters, and on pressure and displacement amplitude changes. Thus, the propagation velocity of a disturbance depends upon its amplitude, as might be expected for a nonlinear process. As a check, the expression for the phase function is evaluated for a poroelastic medium, when the material properties do not depend upon the fluid pressure. In that case, the travel time estimates agree with conventional analytic estimates, and with values calculated using a numerical simulator. For a medium with pressure-dependent permeability I find general agreement between the semi-analytic estimates and estimates from a numerical simulation. In this case the pressure amplitude changes are obtained from the numerical simulator.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Airborne Measurements of Scale‐Dependent Latent Heat Flux Impacted by Water Vapor and Vertical Velocity Over Heterogeneous Land Surfaces During the CHEESEHEAD19 Campaign

Abstract The water vapor transport associated with latent heat flux (LE) in the planetary boundary layer (PBL) is critical for the atmospheric hydrological cycle, radiation balance, and cloud formation. The spatiotemporal variability of LE and water vapor mixing ratio ( r v ) are poorly understood due to the scale‐dependent and nonlinear atmospheric transport responses to land surface heterogeneity. Here, airborne in situ measurements with the wavelet technique are utilized to investigate scale‐dependent relationships among LE, vertical velocity ( w ) variance (), and r v variance () over a heterogeneous surface during the Chequamegon Heterogeneous Ecosystem Energy‐balance Study Enabled by a High‐density Extensive Array of Detectors 2019 (CHEESEHEAD19) field campaign. Our findings reveal distinct scale distributions of LE, , and at 100 m height, with a majority scale range of 120 m–4 km in LE, 32 m–2 km in , and 200 m–8 km in . The scales are classified into three scale ranges, the turbulent scale (8–200 m), large‐eddy scale (200 m–2 km), and mesoscale (2–8 km) to evaluate scale‐resolved LE contributed by and . The large‐eddy scale in PBL contributes over 70% of the monthly mean total LE with equal parts (50%) of contributions from and . The monthly temporal variations mainly come from the first two major contributing classified scales in LE, , and . These results confirm the dominant role of the large‐eddy scale in the PBL in the vertical moisture transport from the surface to the PBL, while the mesoscale is shown to contribute an additional ∼20%. This analysis complements published scale‐dependent LE variations, which lack detailed scale‐dependent vertical velocity and moisture information.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals

Methylammonium lead iodide perovskite has attracted considerable recent interest for solution processable solar cells and other optoelectronic applications. The orthorhombic-to-tetragonal phase transition in perovskite can significantly alter its optical, electrical properties and impact the corresponding applications. Here, we report a systematic investigation of the size-dependent orthorhombic-to-tetragonal phase transition using a combined temperature-dependent optical, electrical transport and transmission electron microscopy study. Our studies of individual perovskite microplates with variable thicknesses demonstrate that the phase transition temperature decreases with reducing microplate thickness. The sudden decrease of mobility around phase transition temperature and the presence of hysteresis loops in the temperature-dependent mobility confirm that the orthorhombic-to-tetragonal phase transition is a first-order phase transition. Lastly, our findings offer significant fundamental insight on the temperature-and size-dependent structural, optical and charge transport properties of perovskite materials, and can greatly impact future exploration of novel electronic and optoelectronic devices from these materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Changing expression patterns of TonB-dependent transporters suggest shifts in polysaccharide consumption over the course of a spring phytoplankton bloom

Algal blooms produce large quantities of organic matter that is subsequently remineralised by bacterial heterotrophs. Polysaccharide is a primary component of algal biomass. It has been hypothesised that individual bacterial heterotrophic niches during algal blooms are in part determined by the available polysaccharide substrates present. Measurement of the expression of TonB-dependent transporters, often specific for polysaccharide uptake, might serve as a proxy for assessing bacterial polysaccharide consumption over time. To investigate this, we present here high-resolution metaproteomic and metagenomic datasets from bacterioplankton of the 2016 spring phytoplankton bloom at Helgoland island in the southern North Sea, and expression profiles of TonB-dependent transporters during the bloom, which demonstrate the importance of both the Gammaproteobacteria and the Bacteroidetes as degraders of algal polysaccharide. TonB-dependent transporters were the most highly expressed protein class, split approximately evenly between the Gammaproteobacteria and Bacteroidetes , and totalling on average 16.7% of all detected proteins during the bloom. About 93% of these were predicted to take up organic matter, and for about 12% of the TonB-dependent transporters, we predicted a specific target polysaccharide class. Most significantly, we observed a change in substrate specificities of the expressed transporters over time, which was not reflected in the corresponding metagenomic data. From this, we conclude that algal cell wall-related compounds containing fucose, mannose, and xylose were mostly utilised in later bloom stages, whereas glucose-based algal and bacterial storage molecules including laminarin, glycogen, and starch were used throughout. Quantification of transporters could therefore be key for understanding marine carbon cycling.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2017

Temperature Dependence in Heterogeneous Nucleation with Application to the Direct Determination of Cluster Energy on Nearly Molecular Scale

A re-examination of measurements of heterogeneous nucleation of water vapor on silver nanoparticles is presented here using a model-free framework that derives the energy of critical cluster formation directly from measurements of nucleation probability. Temperature dependence is correlated with cluster stabilization by the nanoparticle seed and previously found cases of unusual increasing nucleation onset saturation ratio with increasing temperature are explained. A necessary condition for the unusual positive temperature dependence is identified, namely that the critical cluster be more stable, on a per molecule basis, than the bulk liquid to exhibit the effect. Temperature dependence is next examined in the classical Fletcher model, modified here to make the energy of cluster formation explicit in the model. The contact angle used in the Fletcher model is identified as the microscopic contact angle, which can be directly obtained from heterogeneous nucleation experimental data by a recently developed analysis method. Here an equivalent condition, increasing contact angle with temperature, is found necessary for occurrence of unusual temperature dependence. Our findings have immediate applications to atmospheric particle formation and nanoparticle detection in condensation particle counters (CPCs).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

A pyridoxal 5'-phosphate-dependent Mannich cyclase

Pyridoxal 5'-phosphate (PLP)-dependent enzymes catalyse a diverse range of chemical transformations. Despite their extraordinary functional diversity, no PLP-dependent enzyme is known to catalyse Mannich-type reactions, an important carbon–carbon bond-forming reaction in synthetic organic chemistry. Here we report the discovery of a biosynthetic enzyme LolT, a PLP-dependent enzyme catalysing a stereoselective intramolecular Mannich reaction to construct the pyrrolizidine core scaffold in loline alkaloids. Importantly, its versatile catalytic activity is harnessed for stereoselective synthesis of a variety of conformationally constrained α,α-disubstituted α-amino acids, which bear vicinal quaternary–tertiary stereocentres and various aza(bi)cyclic backbones, such as indolizidine, quinolizidine, pyrrolidine and piperidine. Furthermore, crystallographic and mutagenesis analysis and computational studies together provided mechanistic insights and structural basis for understanding LolT’s catalytic activity and stereoselectivity. As a whole, this work expands the biocatalytic repertoire of carbon–carbon bond-forming enzymes and increases our knowledge of the catalytic versatility of PLP-dependent enzymes.

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

Temperature and solvent-dependent photoluminescence quenching in [Ru(bpy) 2 (bpy-cc-AQ)] 2+

I have herein investigated the solvent-dependent photoluminescence quenching mechanism of [Ru(bpy) 2 (bpy-cc-AQ)] 2+ using variable temperature emission spectroscopies. In this wok, the photophysics of this complex are dominated by an excited-state thermal equilibrium between a photoluminescent 3 MLCT state and a charge-separated state that lies higher in energy relative to the 3 MLCT state in low polarity solvents and approximately isoenergetic in high polarity solvents. Furthermore, an unusual photoluminescence temperature-dependence in high polarity solvents is shown to arise from competition between enthalpic factors favouring the charge-separated state and entropic factors favouring the photoluminescent 3 MLCT state, analogous to the molecular light-switch effect of [Ru(bpy) 2 (dppz)] 2+ . The solvent-dependent photoluminescence quenching of [Ru(bpy)2(bpy-cc-AQ)] 2+ is attributed to two key solvent-dependent factors: (1) the excited-state equilibrium position and (2) the rate of charge-recombination from the charge-separated state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Mass dependency of turbulent parameters in stationary glow discharge plasmas

A direct current glow discharge tube is used to determine how mass changes the effects of certain turbulence characteristics in a weakly ionized gas. Helium, neon, argon, and krypton plasmas were created, and an axial magnetic field, varied from 0.0 to 550.0 Gauss, was used to enhance mass dependent properties of turbulence. From the power spectra of light emission variations associated with velocity fluctuations, determination of mass dependency on turbulent characteristic unstable modes, energy associated with turbulence, and the rate at which energy is transferred from scale to scale are measured. The magnetic field strength is found to be too weak to overcome particle diffusion to the walls to affect the turbulence in all four types of plasmas, though mass dependency is still detected. Though the total energy and the rate at which the energy moves between scales are mass invariant, the amplitude of the instability modes that characterize each plasma are dependent on mass.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

Angular dependence of anisotropic magnetoresistance in magnetic systems

Anisotropic magnetoresistance (AMR), whose physical origin is attributed to the combination of spin dependent scattering and spin orbital coupling (SOC), usually displays simple angular dependence for polycrystalline ferromagnetic metals. By including generic spin dependent scattering and spin Hall (SH) terms in the Ohm's law, we explicitly show that various magneto-transport phenomena such as anomalous Hall (AH), SH, planar Hall (PH) and AMR could be quantitatively related for bulk polycrystalline ferromagnetic metals. We also discuss how AMR angular dependence is affected by the presence of interfacial SOC in magnetic layered structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Spin-dependent delay time in ferromagnet/insulator/ferromagnet heterostructures

We study theoretically spin-dependent group delay and dwell time in ferromagnet/insulator/ferromagnet (FM/I/FM) heterostructure. The results indicate that, when the electrons with different spin orientations tunnel through the FM/I/FM junction, the spin-up process and the spin-down process are separated on the time scales. As the self-interference delay has the spin-dependent features, the variations of spin-dependent dwell-time and spin-dependent group-delay time with the structure parameters appear different features, especially, in low incident energy range. These different features show up as that the group delay times for the spin-up electrons are always longer than those for spin-down electrons when the barrier height or incident energy increase. In contrast, the dwell times for the spin-up electrons are longer (shorter) than those for spin-down electrons when the barrier heights (the incident energy) are under a certain value. When the barrier heights (the incident energy) exceed a certain value, the dwell times for the spin-up electrons turn out to be shorter (longer) than those for spin-down electrons. In addition, the group delay time and the dwell time for spin-up and down electrons also relies on the comparative direction of magnetization in two FM layers and tends to saturation with the thickness of the barrier.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Spin-dependent terahertz oscillator based on hybrid graphene superlattices

We theoretically study the occurrence of Bloch oscillations in biased hybrid graphene systems with spin-dependent superlattices. The spin-dependent potential is realized by a set of ferromagnetic insulator strips deposited on top of a gapped graphene nanoribbon, which induce a proximity exchange splitting of the electronic states in the graphene monolayer. We numerically solve the Dirac equation and study Bloch oscillations in the lowest conduction band of the spin-dependent superlattice. While the Bloch frequency is the same for both spins, we find the Bloch amplitude to be spin dependent. This difference results in a spin-polarized ac electric current in the THz range.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Modelling non-adiabatic effects in H{sub 3}{sup +}: Solution of the rovibrational Schrödinger equation with motion-dependent masses and mass surfaces

Introducing different rotational and vibrational masses in the nuclear-motion Hamiltonian is a simple phenomenological way to model rovibrational non-adiabaticity. It is shown on the example of the molecular ion H{sub 3}{sup +}, for which a global adiabatic potential energy surface accurate to better than 0.1 cm{sup −1} exists [M. Pavanello, L. Adamowicz, A. Alijah, N. F. Zobov, I. I. Mizus, O. L. Polyansky, J. Tennyson, T. Szidarovszky, A. G. Császár, M. Berg et al., Phys. Rev. Lett. 108, 023002 (2012)], that the motion-dependent mass concept yields much more accurate rovibrational energy levels but, unusually, the results are dependent upon the choice of the embedding of the molecule-fixed frame. Correct degeneracies and an improved agreement with experimental data are obtained if an Eckart embedding corresponding to a reference structure of D{sub 3h} point-group symmetry is employed. The vibrational mass of the proton in H{sub 3}{sup +} is optimized by minimizing the root-mean-square (rms) deviation between the computed and recent high-accuracy experimental transitions. The best vibrational mass obtained is larger than the nuclear mass of the proton by approximately one third of an electron mass, m{sub opt,p}{sup (v)}=m{sub nuc,p}+0.31224 m{sub e}. This optimized vibrational mass, along with a nuclear rotational mass, reduces the rms deviation of the experimental and computed rovibrational transitions by an order of magnitude. Finally, it is shown that an extension of the algorithm allowing the use of motion-dependent masses can deal with coordinate-dependent mass surfaces in the rovibrational Hamiltonian, as well.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Theoretical study of a screened Hartree–Fock exchange potential using position-dependent atomic dielectric constants

Dielectric-dependent screened Hartree–Fock (HF) exchange potential and Slater-formula have been reported, where the ratio of the HF exchange term mixed into potentials is inversely proportional to the dielectric constant of the target semiconductor. This study introduces a position-dependent dielectric constant method in which the dielectric constant is partitioned between the atoms in a semiconductor. These partitioned values differ depending on the electrostatic environment surrounding the atoms and lead to position-dependent atomic dielectric constants. These atomic dielectric constants provide atomic orbital-based matrix elements for the screened exchange potentials. Energy band structures of several semiconductors and insulators are also presented to validate this approach.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Effect of super-exchange interaction on ground state magnetic properties of spin-dependent Falicov-Kimball model on a triangular lattice

Ground state magnetic properties are studied by incorporating the super-exchange interaction (J{sub se}) in the spin-dependent Falicov-Kimball model (FKM) between localized (f-) electrons on a triangular lattice for half filled case. Numerical diagonalization and Monte-Carlo simulation are used to study the ground state magnetic properties. We have found that the magnetic moment of (d-) and (f-) electrons strongly depend on the value of Hund’s exchange (J), super-exchange interaction (J{sub se}) and also depends on the number of (d-) electrons (N{sub d}). The ground state changes from antiferromagnetic (AFM) to ferromagnetic (FM) state as we decrease (N{sub d}). Also the density of d electrons at each site depends on the value of J and J{sub se}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Current-perpendicular-to-the-plane magnetoresistance from large interfacial spin-dependent scattering between Co{sub 50}Fe{sub 50} magnetic layer and In-Zn-O conductive oxide spacer layer

We have investigated electrically conductive indium-zinc-oxide (IZO) deposited by magnetron sputtering as spacer layer for current-perpendicular-to-the-plane giant magnetoresistance sensor devices. Spin-valves with a Co{sub 50}Fe{sub 50}/IZO/Co{sub 50}Fe{sub 50} trilayer showed resistance-area product (RA) ranging from 110 to 250 mΩ μm{sup 2}, significantly larger than all-metal structures with Ag or Cu spacers (∼40 mΩ μm{sup 2}). Magnetoresistance ratios (ΔR/R) of 2.5% to 5.5% depending on the IZO spacer thickness (1.5–6.0 nm), corresponding to ΔRA values from 3 to 13 mΩ μm{sup 2}, were obtained. The values of ΔRA with the IZO spacers and Co{sub 50}Fe{sub 50} magnetic layers were significantly larger than those with conventional metal spacers and Co{sub 50}Fe{sub 50} magnetic layers (∼1–2 mΩ μm{sup 2}). The dependence of ΔRA on the magnetic layer thickness suggests that the larger ΔRA obtained with IZO spacer is due to a large interfacial spin-dependent scattering caused by the large specific resistance at the Co{sub 50}Fe{sub 50}/IZO interface. From structural characterization by TEM and the observed dependence of the RA dispersion on device size, the electric current flowing through the IZO spacer is thought to be laterally uniform, similar to normal metal spacers.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗