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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 811 records · Page 45
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Non-perturbative many-body treatment of molecular magnets

Molecular magnets have received significant attention because of their potential applications in quantum information and quantum computing. A delicate balance of electron correlation, spin–orbit coupling (SOC), ligand field splitting, and other effects produces a persistent magnetic moment within each molecular magnet unit. The discovery and design of molecular magnets with improved functionalities would be greatly aided by accurate computations. However, the competition among the different effects poses a challenge for theoretical treatments. Electron correlation plays a central role since d- or f-element ions, which provide the magnetic states in molecular magnets, often require explicit many-body treatments. SOC, which expands the dimensionality of the Hilbert space, can also lead to non-perturbative effects in the presence of strong interaction. Furthermore, molecular magnets are large, with tens of atoms in even the smallest systems. We show how an ab initio treatment of molecular magnets can be achieved with auxiliary-field quantum Monte Carlo, in which electron correlation, SOC, and material specificity are included accurately and on an equal footing. Furthermore, the approach is demonstrated by an application to compute the zero-field splitting of a locally linear Co 2+ complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2017

High Density Packaging Technologies for RF Electronics in Small Spacecraft

This paper will describe a few high density packaging technologies which we are currently exploring for use in current and future small spacecraft applications. The three categories of technologies include organic multichip modules (MCMs), ceramic leadless surface mount technology (SMT) and 3D printed waveguide structures. There are many other packaging technologies that currently exist but these three were selected in part due to their long heritage in various commercial, military and space applications along with each having a relatively clear path to flight. For each of these technologies, detailed examples will be included in which hardware has been fabricated and tested for use in RF electronics for spacecraft transponders. The organic MCM example will be described in most detail and it utilizes a packaging technology by the name of CoreEZ which is a trademark of i3 Electronics. This MCM has shrunk a portion of our electronics down to 1/8th of its previous area. The CoreEZ technology has been shown to be rad hard beyond a total ionizing dose (TID) of 300kRad and the MCM which was fabricated has gone through thermal cycling and shown to have no degradation in performance. The ceramic leadless package examples include packages from high reliability manufactures by the name of KCB solutions and Barry Industries. In the case of KCB solutions, we have multiple products that will be described including a hermetic ceramic carrier which houses three microwave monolithic integrated circuits (MMICs) along with small discrete components. Finally, we will discuss the results of our search for a 3D printing process that allows us to reduce the cost and volume of our waveguide filters and diplexers for low cost small satellite applications. We have fabricated a few prototypes using direct metal laser sintering (DMLS) and metal coated plastics. Each of these packaging technology discussions will have a brief overview of its current and future use.

Aquirre, Fernando↗
NASA NTRS2016

High Density Packaging Technologies for RF Electronics in Small Spacecraft

This paper will describe a few high density packaging technologies which we are currently exploring for use in current and future small spacecraft applications. The three categories of technologies include organic multichip modules (MCMs), ceramic leadless surface mount technology (SMT) and 3D printed waveguide structures. There are many other packaging technologies that currently exist but these three were selected in part due to their long heritage in various commercial, military and space applications along with each having a relatively clear path to flight. For each of these technologies, detailed examples will be included in which hardware has been fabricated and tested for use in RF electronics for spacecraft transponders. The organic MCM example will be described in most detail and it utilizes a packaging technology by the name of CoreEZ which is a trademark of i3 Electronics. This MCM has shrunk a portion of our electronics down to 1/8th of its previous area. The CoreEZ technology has been shown to be rad hard beyond a total ionizing dose (TID) of 300kRad and the MCM which was fabricated has gone through thermal cycling and shown to have no degradation in performance. The ceramic leadless package examples include packages from high reliability manufactures by the name of KCB solutions and Barry Industries. In the case of KCB solutions, we have multiple products that will be described including a hermetic ceramic carrier which houses three microwave monolithic integrated circuits (MMICs) along with small discrete components. Finally, we will discuss the results of our search for a 3D printing process that allows us to reduce the cost and volume of our waveguide filters and diplexers for low cost small satellite applications. We have fabricated a few prototypes using direct metal laser sintering (DMLS) and metal coated plastics. Each of these packaging technology discussions will have a brief overview of its current and future use.

Schatzel, Donald↗
DOE OSTI2021

Mesoscale Confinement Effects and Emergent Quantum Interference in Titania Antidot Thin Films

The effect of confinement on electron and ion transport in oxide films is of interest both fundamentally and technologically for the design of next-generation electronic devices. In metal oxides with mobile ions and vacancies, it is the interplay of the different modes of charge transport and the corresponding current–voltage signatures that is of interest. We developed a patterned structure in titania films, with feature sizes of 11–20 nm, that allow us to explore confined transport. In this study, we describe how confinement changes the competing charge transport mechanisms, the patterned antidot array leads to displacement fields and confines the charge density that results in modified and emergent electron transport with an increase in conductivity. This emergent behavior can be described by considering electron interference effects. Characterization of the charge transport with electron holography and impedance spectroscopy, and through comparison with modeling, show that nanoscale confinement is a way to control quantum interference.

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

Magnetically Induced Binary Ferrocene with Oxidized Iron

Ferrocene is perhaps the most popular and well-studied organometallic molecule, but our understanding of its structure and electronic properties has not changed for more than 70 years. In particular, all previous attempts of chemically oxidizing pure ferrocene by binding directly to the iron center have been unsuccessful, and no significant change in structure or magnetism has been reported. Here, using a metal organic framework host material, we were able to fundamentally change the electronic and magnetic structure of ferrocene to take on a never-before observed physically stretched/bent high-spin Fe(II) state, which readily accepts O 2 from air, chemically oxidizing the iron from Fe(II) to Fe(III). We also show that the binding of oxygen is reversible through temperature swing experiments. Our analysis is based on combining Mößbauer spectroscopy, extended X-ray absorption fine structure, in situ infrared, SQUID, thermal gravimetric analysis, and energy dispersive X-ray fluorescence spectroscopy measurements with ab initio modeling.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Methane Activation by a Mononuclear Copper Active Site in the Zeolite Mordenite: Effect of Metal Nuclearity on Reactivity

The direct conversion of methane to methanol would have a wide reaching environmental and industrial impact. Copper-containing zeolites can perform this reaction at low temperatures and pressures at a previously defined O 2 -activated [Cu 2 O] 2+ site. However, after autoreduction of the copper-containing zeolite mordenite and removal of the [Cu 2 O] 2+ active site, the zeolite is still methane reactive. In this study, we use diffuse reflectance UV–vis spectroscopy, magnetic circular dichroism, resonance Raman spectroscopy, electron paramagnetic resonance, and X-ray absorption spectroscopy to unambiguously define a mononuclear [CuOH] + as the CH 4 reactive active site of the autoreduced zeolite. The rigorous identification of a mononuclear active site allows a reactivity comparison to the previously defined [Cu 2 O] 2+ active site. We perform kinetic experiments to compare the reactivity of the [CuOH] + and [Cu 2 O] 2+ sites and find that the binuclear site is significantly more reactive. From the analysis of density functional theory calculations, we elucidate that this increased reactivity is a direct result of stabilization of the [Cu 2 OH] 2+ H-atom abstraction product by electron delocalization over the two Cu cations via the bridging ligand. This significant increase in reactivity from electron delocalization over a binuclear active site provides new insights for the design of highly reactive oxidative catalysts.

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

Benchmark Data Set of Crystalline Organic Semiconductors

This work reports a Benchmark Data set of Crystalline Organic Semiconductors to test calculations of the structural and electronic properties of these materials in the solid state. The data set contains 67 crystals consisting of mostly rigid molecules with a single dominant conformer, covering the majority of known structural types. The experimental crystal structure is available for the entire data set, whereas zero-temperature unit cell volume can be reliably estimated for a subset of 28 crystals. Using this subset, we benchmark r 2 SCAN-D3 and PBE-D3 density functionals. Then, for the entire data set, we benchmark approximate density functional theory (DFT) methods, including GFN1-xTB and DFTB3(3ob-3-1), with various dispersion corrections against r 2 SCAN-D3. Our results show that r 2 SCAN-D3 geometries are accurate within a few percent, which is comparable to the statistical uncertainty of experimental data at a fixed temperature, but the unit cell volume is systematically underestimated by 2% on average. The several times faster PBE-D3 provides an unbiased estimate of the volume for all systems except for molecules with highly polar bonds, for which the volume is substantially overestimated in correlation with the underestimation of atomic charges. Considered approximate DFT methods are orders of magnitude faster and provide qualitatively correct but overcompressed crystal structures unless the dispersion corrections are fitted by unit cell volume.

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

Synthesis and Self-Assembly of Monodisperse Graphene Nanoribbons: Access to Submicron Architectures with Long-Range Order and Uniform Orientation

Fabricating organic semiconducting materials into large-scale well-organized architectures is critical for building high performance molecular electronics. While graphene nanoribbons (GNRs) hold enormous promise for various device applications, their assembly into a well-structured monolayer or multilayer architecture poses a substantial challenge. Here we report the preparation of length-defined monodisperse GNRs via the integrated iterative binomial synthesis (IIBS) strategy and their self-assembly into submicron-architectures with long-range order, uniform orientation as well as regular layers. Further, the use of short alkyl side chains benefits forming stable multi-layers through interlocking structures. By changing the length and backbone shapes of these monodisperse GNRs, various three-dimensional assemblies including multilayer stripes, monolayer stripes, and nanowires, can be achieved, leading to different photophysical properties and band gaps. The discovery of these intriguing self-assembly behaviors of length-defined GNRs is expected to open the door for various future applications.

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

Deviatoric stress-induced metallization, layer reconstruction and collapse of van der Waals bonded zirconium disulfide

In contrast to two-dimensional (2D) monolayer materials, van der Waals layered transition metal dichalcogenides exhibit rich polymorphism, making them promising candidates for novel superconductor, topological insulators and electrochemical catalysts. Here, we highlight the role of hydrostatic pressure on the evolution of electronic and crystal structures of layered ZrS2. Under deviatoric stress, our electrical experiments demonstrate a semiconductor-to-metal transition above 30.2 GPa, while quasi-hydrostatic compression postponed the metallization to 38.9 GPa. Both X-ray diffraction and Raman results reveal structural phase transitions different from those under hydrostatic pressure. Under deviatoric stress, ZrS2 rearranges the original ZrS6 octahedra into ZrS8 cuboids at 5.5 GPa, in which the unique cuboids coordination of Zr atoms is thermodynamically metastable. The structure collapses to a partially disordered phase at 17.4 GPa. These complex phase transitions present the importance of deviatoric stress on the highly tunable electronic properties of ZrS2 with possible implications for optoelectronic devices.

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

Role of Protein-Water Interface in the Stacking Interactions of Granum Thylakoid Membranes—As Revealed by the Effects of Hofmeister Salts

The thylakoid membranes of vascular plants are differentiated into stacked granum and unstacked stroma regions. The formation of grana is triggered by the macrodomain formation of photosystem II and light-harvesting complex II (PSII-LHCII) and thus their lateral segregation from the photosystem I—light-harvesting complex I (PSI-LHCI) super-complexes and the ATP-synthase; which is then stabilized by stacking interactions of the adjacent PSII-LHCII enriched regions of the thylakoid membranes. The self-assembly and dynamics of this highly organized membrane system and the nature of forces acting between the PSII-LHCII macrodomains are not well understood. By using circular dichroism (CD) spectroscopy, small-angle neutron scattering (SANS) and transmission electron microscopy (TEM), we investigated the effects of Hofmeister salts on the organization of pigment-protein complexes and on the ultrastructure of thylakoid membranes. We found that the kosmotropic agent (NH 4 ) 2 SO 4 and the Hofmeister-neutral NaCl, up to 2 M concentrations, hardly affected the macro-organization of the protein complexes and the membrane ultrastructure. In contrast, chaotropic salts, NaClO 4 , and NaSCN destroyed the mesoscopic structures, the multilamellar organization of the thylakoid membranes and the chiral macrodomains of the protein complexes but without noticeably affecting the short-range, pigment-pigment excitonic interactions. Comparison of the concentration- and time-dependences of SANS, TEM and CD parameters revealed the main steps of the disassembly of grana in the presence of chaotropes. It begins with a rapid diminishment of the long-range periodic order of the grana membranes, apparently due to an increased stacking disorder of the thylakoid membranes, as reflected by SANS experiments. SANS measurements also allowed discrimination between the cationic and anionic effects—in stacking and disorder, respectively. This step is followed by a somewhat slower disorganization of the TEM ultrastructure, due to the gradual loss of stacked membrane pairs. Occurring last is the stepwise decrease and disappearance of the long-range chiral order of the protein complexes, the rate of which was faster in LHCII-deficient membranes. These data are interpreted in terms of a theory, from our laboratory, according to which Hofmeister salts primarily affect the hydrophylic-hydrophobic interactions of proteins, and the stroma-exposed regions of the intrinsic membrane proteins, in particular—pointing to the role of protein-water interface in the stacking interactions of granum thylakoid membranes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Non-ideal stoichiometry and thermochemistry of aqueous iridium oxide nanoparticles in proton-coupled electron transfer and oxygen-atom transfer

Reported here are reactions of aqueous colloidal IrO x nanoparticles (NPs) with proton-coupled electron transfer (PCET) and oxygen-atom transfer (OAT) organic reagents, determining the reaction stoichiometries and thermochemistry. IrO x NPs have attracted much attention for their high electrocatalytic activity, but understanding of their fundamental reaction chemistry is limited. This IrO x NP model system is simple, with UV-vis titrations demonstrating reversible interconversion between predominantly Ir IV and predominantly Ir III NPs. This simplicity allows studies that reveal their complex non-idealities. The NP redox chemistry has a “super-Nernstian” stoichiometry of ∼1.3H + per 1e − transferred during both PCET and OAT reactions, as measured with electrochemistry and chemical methods. Spectroelectrochemistry revealed a broad distribution of surface IrO x –H bond dissociation free energies (BDFEs), becoming weaker as more H is added. Such variation in binding strengths—a non-ideal binding isotherm—is common for surface adsorbates. For IrO x , the variation of BDFE(IrO–H)s is fit well to a Frumkin isotherm with a width of 6.5 kcal mol −1 . For OAT from the reactive oxygen atoms of IrO x NPs, bracketing experiments gave 93 ± 24 kcal mol −1 for the average BDFE(O x Ir–O), with a predicted spread much larger than that for the BDFE(IrO–H). Taken together, the results show the importance of non-ideal stoichiometry and thermochemistry for IrO x NPs, and they open a path to more complete models to understand catalytic redox reactions at such surfaces.

Iridium Oxide Nanoparticles (NPs)↗
DOE OSTI2021

Modulation of π-stacking modes and photophysical properties of an organic semiconductor through isosteric cocrystallization

We report on the control of π-stacking modes (herringbone vs slipped-stack) and photophysical properties of 9,10-bis((E)-2-(pyridin-4-yl)vinyl)anthracene (BP4VA), an anthracene-based organic semiconductor (OSC), by isosteric cocrystallization (i.e., the replacement of one functional group in a coformer with another of “similar” electronic structure) with 2,4,6-trihalophenols (3X-ph-OH, where X = Cl, Br, and I). Specifically, BP4VA organizes as slipped-stacks when cocrystallized with 3Cl-ph-OH and 3Br-ph-OH, while cocrystallization with 3I-ph-OH results in a herringbone mode. The photoluminescence and molecular frontier orbital energy levels of BP4VA were effectively modulated by the presence of 3X-ph-OH through cocrystallization. We envisage that the cocrystallization of OSCs with minimal changes in cocrystal formers can provide access to convenient structural and property diversification for advanced single-crystal electronics.

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

Tensor Hypercontraction of Cluster Perturbation Theory: Quartic Scaling Perturbation Series for the Coupled Cluster Singles and Doubles Ground-State Energies

Even though Cluster Perturbation has been shown to be a robust non-iterative alternative to Coupled Cluster Theory, it is still plagued by high order polynomial computational scaling and the storage of higher order tensors. Here we present a proof-of-concept strategy for implementing Cluster Perturbation Theory ground state energy series for the coupled cluster singles and doubles energy with N 4 computational scaling using Tensor Hypercontraction (THC). The reduction in computational scaling by two orders is achieved by decomposing two electron repulsion integrals, doubles amplitudes and multipliers, as well as selected doubles intermediates to Tensor Hypercontraction format. Using the outlined strategy, we showcase that the Tensor Hypercontraction pilot implementations retain numerical accuracy to within 1 kcal/mol relative to corresponding conventional and density fitting implementations and we empirically verify the N 4 scaling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

The Titan haze revisted: Magnetospheric energy sorces quantitative tholin yields

We present laboratory measurements of the radiation yields of complex organic solids produced from N2/CH4 gas mixtures containing 10 or 0.1% CH4. These tholins are thought to resemble organic aerosols produced in the atmospheres of Titan, Pluto, and Triton. The tholin yields are large compared to the total yield of gaseous products: nominally, 13 (C + N)/100 eV for Titan tholin and 2.1 (C + N)/100 eV for Triton tholin. High-energy magnetospheric electrons responsible for tholin production represents a class distinct from the plasma electrons considered in models of Titan's aiglow. Electrons with E greater than 20 keV provide an energy flux approximately 1 x 10(exp -2) erg/cm/sec, implying from our measured tholin yields a mass flux of 0.5 to 4.0 x 10(exp -14) g/sq cm/sec of tholin. (The corresponding thickness of the tholin sedimentary column accumulated over 4 Gyr on Titan's surface is 4 to 30 m). This figure is in agreement with required mass fluxes computed from recent radiative transfer and sedimentation models. If, however, theses results, derived from experiments at approximately 2 mb, are applied to lower pressure levels toward peak auroral electron energy deposition and scaled with pressure as the gas-phase organic yields, the derived tholin mass flux is at least an order of magnitude less. We attrribute this difference to the fact that tholin synthesis occurs well below the level of maximum electron energy depositon and to possible contributions to tholis from UV-derived C2-hydrocarbons. We conclude that Tita tholin, produced by magnetospheric electrons, is alone sufficient to supply at least a significant fraction of Titan's haze-a result consistent with the fact that the optical properties of Titan tholin, among all proposed material, are best at reproducing Titan's geometric albedo spectrum from near UV to mid-IR in light-scattering models.

Thompson, W. Reid↗
NASA NTRS1994

The Titan haze revisited: magnetospheric energy sources and quantitative tholin yields

We present laboratory measurements of the radiation yields of complex organic solids produced from N2/CH4 gas mixtures containing 10 or 0.1% CH4. These tholins are thought to resemble organic aerosols produced in the atmospheres of Titan, Pluto, and Triton. The tholin yields are large compared to the total yield of gaseous products: nominally, 13 (C + N)/100 eV for Titan tholin and 2.1 (C + N)/100 eV for Triton tholin. High-energy magnetospheric electrons responsible for tholin production represent a class distinct from the plasma electrons considered in models of Titan's airglow. Electrons with E > 20 keV provide an energy flux approximately 1 x 10(-2) erg cm-2 sec-1, implying from our measured tholin yields a mass flux of 0.5 to 4.0 x 10(-14) g cm-2 sec-1 of tholin. (The corresponding thickness of the tholin sedimentary column accumulated over 4 Gyr on Titan's surface is 4 to 30 m.) This figure is in agreement with required mass fluxes computed from recent radiative transfer and sedimentation models. If, however, these results, derived from experiments at approximately 2 mb, are applied to lower pressure levels toward peak auroral electron energy deposition and scaled with pressure as the gas-phase organic yields, the derived tholin mass flux is at least an order of magnitude less. We attribute this difference to the fact that tholin synthesis occurs well below the level of maximum electron energy deposition and to possible contributions to tholins from UV-derived C2-hydrocarbons. We conclude that Titan tholin, produced by magnetospheric electrons, is alone sufficient to supply at least a significant fraction of Titan's haze--a result consistent with the fact that the optical properties of Titan tholin, among all proposed materials, are best at reproducing Titan's geometric albedo spectrum from near UV to mid-IR in light-scattering models.

Non-NASA Center↗
DOE OSTI2020

Iron(II) Complexes of an Anionic Bis(ylide)diphenylborate Ligand

Double deprotonation of the salt [Ph 2 B(PMe 3 ) 2 ][OTf] provides access to a bis(ylide)diphenylborate ligand that is readily transferred in situ to iron(II). Depending on the reaction stoichiometry, both the “ate” complex [Ph 2 B(Me 2 PCH 2 ) 2 Fe(μ-Cl) 2 Li(THF) 2 ] and the homoleptic complex [Ph 2 B(Me 2 PCH 2 ) 2 ] 2 Fe can be prepared from FeCl 2 (THF) 1.5 . Further reaction of with FeCl 2 (THF) 1.5 produces the chloride-bridged dimer [Ph 2 B(Me 2 PCH 2 ) 2 Fe(μ-Cl) 2 Fe(CH 2 PMe 2 ) 2 BPh 2 ]. Attempts to reduce or alkylate provide as the only isolable product, likely a consequence of the low steric hindrance of the bis(ylide)diphenylborate ligand. On the other hand, reaction of with the strong field ligand CN t Bu provides the six-coordinate, diamagnetic complex [Ph 2 B(Me 2 PCH 2 ) 2 Fe(CN t Bu) 4 ][Cl]. Here, the electronic structure calculations for the bis(ylide)diphenylborate ligand and homoleptic complex suggest that the C(ylide) atoms are strong σ-donors with little π-bonding character. These initial results suggest the potential for this bis(ylide)diphenylborate ligand in coordination chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗