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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 1,567 records · Page 87
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Benzene derivatives adsorbed to the Ag(111) surface: Binding sites and electronic structure

Dispersion corrected Density Functional Theory calculations were employed to study the adsorption of benzenes derivatized with functional groups encompassing a large region of the activated/deactivated spectrum to the Ag(111) surface. Benzenes substituted with weak activating or deactivating groups, such as methyl and fluoro, do not have a strong preference for adsorbing to a particular site on the substrate, with the corrugations in the potential energy surface being similar to those of benzene. Strong activating (N(CH{sub 3}){sub 2}) and deactivating (NO{sub 2}) groups, on the other hand, possess a distinct site preference. The nitrogen in the former prefers to lie above a silver atom (top site), but in the latter a hollow hexagonal-closed-packed (H{sub hcp}) site of the Ag(111) surface is favored instead. Benzenes derivatized with classic activating groups donate electron density from their highest occupied molecular orbital to the surface, and those functionalized with deactivating groups withdraw electron density from the surface into orbitals that are unoccupied in the gas phase. For benzenes functionalized with two substituents, the groups that are strongly activating or deactivating control the site preference and the other groups assume sites that are, to a large degree, dictated by their positions on the benzene ring. The relative stabilities of the ortho, meta, and para positional isomers of disubstituted benzenes can, in some cases, be modified by adsorption to the surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Nanoporous Gold as a Platform for a Building Block Catalyst

The porous bulk materials are of great interest in catalysis because they can be employed in heterogeneous gas and liquid phase catalysis, electrocatalysis, and in electrocatalytic sensing. Nanoporous gold gained considerable attraction in this context because it is the prime example of a corrosion-derived nanoporous bulk metal. Moreover, the material was shown to be a very active and selective Au type catalyst for a variety of oxidation reactions. In leveraging the functionalization of the surface of the material with various additives, its catalytic applications can be extended and tuned. In this review, we will summarize recent developments in using nanoporous gold as the platform for the development of high performance catalytic materials by adding metals, metal oxides, and molecular functionalities as building blocks.

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

Binary pseudo-random array (BPRA) for inspection and calibration for cylindrical wavefront interferometry

High-accuracy metrology is vitally important in manufacturing ultra-high-quality free-form mirrors designed to manipulate X-ray light with nanometer-scale wavelengths. However, surface topography measurements are instrument dependent, and without the knowledge of how the instrument performs under the practical usage conditions, the measured data contain some degree of uncertainty. Binary Pseudo Random Array (BPRA) “white noise” artifact are effective and useful for characterizing the Instrument Transfer Function (ITF) of surface topography metrology tools and wavefront measurement instrument. BPRA artifact contains features with all spatial frequencies in the instrument bandpass with equal weight. As a result, power spectral density of the patterns has a deterministic white-noise-like character that allows direct determination of the ITF with uniform sensitivity over the entire spatial frequency range. The application examples include electron microscopes, x-ray microscopes, interferometric microscopes, and large field-of-view Fizeau Interferometers. Furthermore, we will introduce the application of BPRA method to characterizing the ITF of Cylindrical Wavefront Interferometry (CWI), by developing the BPRA artifact which matches the radius of curvature of the cylindrical wavefront. The data acquisition and analysis procedures for different applications of the ITF calibration technique developed are also discussed.

Munechika, K↗
NASA NTRS1976

Atomic oxygen-metal surface studies as applied to mass spectrometer measurements of upper planetary atmospheres

The problem of atomic oxygen loss in mass spectrometer ion sources can be reduced to an understanding of the possible surface interactions between oxygen atoms and the metal surface of the ion source. Results are presented for an experimental study in which an atomic oxygen beam apparatus and a mass spectrometer were used to measure the oxygen atom reflection, recombination, general surface reaction, and occlusion probabilities on six different engineering surfaces as a function of atomic oxygen exposure. The materials studied are gold, Nichrome V, aluminum, titanium, silver, and platinum. The variation in measured reflection probability seems to occur with metals that form oxides, Nichrome V being stable in terms of reflection stability. Recombination is observed an all surfaces except aluminum and platinum. Variation in the complete set of measurements in a single experiment is the result of varying surface conditions.

Sjolander, G. W.↗
DOE OSTI2022

Emerging Modification Technologies of Lignin-based Activated Carbon toward Advanced Applications

Lignin-based activated carbon (LAC) is a promising high-quality functional material due to high surface area, abundant porous structure, and various functional groups. Modification is the most important step to functionalize LAC by altering its porous and chemical properties. Here, this Review summarizes the state-of-the-art modification technologies of LAC toward advanced applications. Promising modification approaches are reviewed to display their effects on the preparation of LAC. The multiscale changes in the porosity and the surface chemistry of LAC are fully discussed. Advanced applications are then introduced to show the potential of LAC for supercapacitor electrode, catalyst support, hydrogen storage, and carbon dioxide capture. Finally, the mechanistic structure-function relationships of LAC are elaborated. These results highlight that modification technologies play a special role in altering the properties and defining the functionalities of LAC, which could be a promising porous carbon material toward industrial applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Comparative time-resolved photoemission from the Cu(100) and Cu(111) surfaces

Motivated by the striking dependence of the valence electronic structure of transition metal surfaces on their crystallographic orientation, and by emerging experiments on laser-assisted extended ultraviolet (XUV) photoemission from solid surfaces, we calculate photoemission spectra from Cu(100) and Cu(111) surfaces as a function of the photoelectron final kinetic energy and the delay between the ionizing attosecond XUV pulse train and assisting infrared (IR) laser pulse. Our numerical simulations predict distinct differences in delay-dependent photoelectron energy distributions and photoemission time delays for Cu(100) and Cu(111) surfaces. Furthermore, these differences can be scrutinized experimentally with existing technology in a suggested in situ comparative RABBITT (reconstruction of attosecond beating by interference of two-photon transitions) configuration by placing the two surfaces on a sliding platform while keeping all optical components and pathlengths fixed. Our calculations also show that the inclusion of the Fresnel-reflected incident IR pulse at the metal-vacuum interface modifies photoelectron spectra and photoemission time delays in a characteristic way that reveals the degree of spatial location of the initial electronic states.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1986

Distribution and state of H2O in the high-latitude shallow subsurface of Mars

The state and distribution of H2O molecules at high latitudes are evaluated numerically with emphasis on the effects of seasonal temperatures on the kinetics of H2O transport. The investigation is carried out with a thermal model for the regolith regions from the surface through the ice interface and an atmospheric model for the H2O vapor density at the surface as a function of latitude. Few differences are found in the state and distribution of H2O whether the regolith is composed of Montmorillonite or basalt. During an obliquity cycle, the average exchanged H2O mass is determined to be in the range 1-20 gr/sq cm over the planetary surface, with a total maximum exchanged volume of 1500 cu km of H2O. The exchanged mass would arise mainly from ground ice in the case of a basalt regolith and from adsorbed H2O with Montmorillonite. Finally, seasonal ice stabilization is expected to occur at latitudes above 40 deg when obliquities exceed 25 deg.

Zent, A. P.↗
NASA NTRS2002

The Effects of Amazon Deforestation on Rainfall

This study begins with the hypothesis that heavily deforested regions will experience increased surface heating, leading to local circulations that will ultimately enhance the rainfall, or at least, change the pattern of diurnal evolution of rainfall. This would be an important finding because several modeling studies have concluded that widespread deforestation would lead to decreased rainfall. Towards that end rain estimates from a combined GOES infrared/TRMM microwave technique were analyzed with respect to percent forest cover from Landsat data (courtesy of TRFIC at Michigan State University) and GOES visible channel data over a deforested area in Rondonia (southwest Brazil). Five 1" x 1" areas of varying forest cover were examined during the onset of the wet season in Amazonia (Aug-Sept), when the effects of the surface would not be dominated by large-scale synoptic weather patterns. Preliminary results revealed that: maximum rainfall fell in most deforested area; heavily forested areas received the least rainfall; cumulus cloud development initiated at borders; the amplitude of the diurnal cycle of precipitation was a function of th surface cover. Further work will be presented detailing effects of land surface cover on the GOES infrared-measured surface heating, GOES visible observed cumulus development, thunderstorm initiation based on the location of temperature minima in the infrared data, and estimated rainfall and its diurnal cycle from a combined GOES/TRMM technique. Rainfall estimates derived from non-geosynchronous microwave observations (i.e. Goddard Profiling Algorithm, GPROF) will also be examined.

Starr, David OC.↗
DOE OSTI2017

Low-rank canonical-tensor decomposition of potential energy surfaces: application to grid-based diagrammatic vibrational Green's function theory

Here, a new method is proposed for a fast evaluation of high-dimensional integrals of potential energy surfaces (PES) that arise in many areas of quantum dynamics. It decomposes a PES into a canonical low-rank tensor format, reducing its integral into a relatively short sum of products of low-dimensional integrals. The decomposition is achieved by the alternating least squares (ALS) algorithm, requiring only a small number of single-point energy evaluations. Therefore, it eradicates a force-constant evaluation as the hotspot of many quantum dynamics simulations and also possibly lifts the curse of dimensionality. This general method is applied to the anharmonic vibrational zero-point and transition energy calculations of molecules using the second-order diagrammatic vibrational many-body Green's function (XVH2) theory with a harmonic-approximation reference. In this application, high dimensional PES and Green's functions are both subjected to a low-rank decomposition. Evaluating the molecular integrals over a low-rank PES and Green's functions as sums of low-dimensional integrals using the Gauss–Hermite quadrature, this canonical-tensor-decomposition-based XVH2 (CT-XVH2) achieves an accuracy of 0.1 cm -1 or higher and nearly an order of magnitude speedup as compared with the original algorithm using force constants for water and formaldehyde.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2018

Fabricating Reactive Surfaces with Brush-like and Crosslinked Films of Azlactone-Functionalized Block Co-Polymers

Here in this work, fabrication methods that generate novel surfaces using the azlactone-based block co-polymer, poly (glycidyl methacrylate)-block-poly (vinyl dimethyl azlactone) (PGMA-b-PVDMA), are presented. Due to the high reactivity of azlactone groups towards amine, thiol, and hydroxyl groups, PGMA-b-PVDMA surfaces can be modified with secondary molecules to create chemically or biologically functionalized interfaces for a variety of applications. Previous reports of patterned PGMA-b-PVDMA interfaces have used traditional top-down patterning techniques that generate non-uniform films and poorly controlled background chemistries. Here, we describe customized patterning techniques that enable precise deposition of highly uniform PGMA-b-PVDMA films in backgrounds that are chemically inert or that have biomolecule-repellent properties. Importantly, these methods are designed to deposit PGMA-b-PVDMA films in a manner that completely preserves azlactone functionality through each processing step. Patterned films show well-controlled thicknesses that correspond to polymer brushes (~90 nm) or to highly crosslinked structures (~1-10 μm). Brush patterns are generated using either the parylene lift-off or interface directed assembly methods described and are useful for precise modulation of overall chemical surface reactivity by adjusting either the PGMA-b-PVDMA pattern density or the length of the VDMA block. In contrast, the thick, crosslinked PGMA-b-PVDMA patterns are obtained using a customized micro-contact printing technique and offer the benefit of higher loading or capture of secondary material due to higher surface area to volume ratios. Lastly, detailed experimental steps, critical film characterizations, and trouble-shooting guides for each fabrication method are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2013

HerMES: A DEFICIT IN THE SURFACE BRIGHTNESS OF THE COSMIC INFRARED BACKGROUND DUE TO GALAXY CLUSTER GRAVITATIONAL LENSING

We have observed four massive galaxy clusters with the SPIRE instrument on the Herschel Space Observatory and measure a deficit of surface brightness within their central region after removing detected sources. We simulate the effects of instrumental sensitivity and resolution, the source population, and the lensing effect of the clusters to estimate the shape and amplitude of the deficit. The amplitude of the central deficit is a strong function of the surface density and flux distribution of the background sources. We find that for the current best fitting faint end number counts, and excellent lensing models, the most likely amplitude of the central deficit is the full intensity of the cosmic infrared background (CIB). Our measurement leads to a lower limit to the integrated total intensity of the CIB of I{sub 250{mu}m}>0.69{sub -0.03}{sup +0.03}(stat.){sub -0.06}{sup +0.11}(sys.) MJy sr{sup -1}, with more CIB possible from both low-redshift sources and from sources within the target clusters. It should be possible to observe this effect in existing high angular resolution data at other wavelengths where the CIB is bright, which would allow tests of models of the faint source component of the CIB.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1988

Summary of along-track data from the Earth radiation budget satellite for several major desert regions

For several days in January and August 1985, the Earth Radiation Budget Satellite, a component of the Earth Radiation Budget Experiment (ERBE), was operated in an along-track scanning mode. A survey of radiance measurements is given for four desert areas in Africa, the Arabian Peninsula, Australia, and the Sahel region of Africa. Each overflight provides radiance information for four scene categories: clear, partly cloudy, mostly cloudy, and overcast. The data presented include the variation of radiance in each scene classification as a function of viewing zenith angle during each overflight of the five target areas. Several features of interest in the development of anisotropic models are evident, including day-night differences in longwave limb darkening and the azimuthal dependence of short wave radiance. There is some evidence that surface features may introduce thermal or visible shadowing that is not incorporated in the usual descriptions of the anisotropic behavior of radiance as viewed from space. The data also demonstrate that the ERBE scene classification algorithms give results that, at least for desert surfaces, are a function of viewing geometry.

Brooks, David R.↗
DOE OSTI2016

Balmer-α spectrum measurements of the LHD one-third ion source

Wavelength spectra of Balmer-α light from plasmas in the extraction region of the Large Helical Device-R&D negative ion source, or the LHD one-third ion source have exhibited a blue shift as a negative bias voltage was applied to the plasma grid. The blue shift increased as the negative bias voltage with respect to the local plasma potential was increased. The measured spectra were compared with the velocity distributions of surface reflected hydrogen atoms calculated by atomic collisions in amorphous target code. The arc power and the source H{sub 2} pressure also affected the shift and broadening in the observed Balmer-α spectra. The possibility of identifying the negative hydrogen ions produced at the low work function plasma grid surface by high resolution spectroscopy is discussed.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2012

Real-time Studies of Battery Electrochemical Reactions Inside a Transmission Electron Microscope

We report the development of new experimental capabilities and ab initio modeling for real-time studies of Li-ion battery electrochemical reactions. We developed three capabilities for in-situ transmission electron microscopy (TEM) studies: a capability that uses a nanomanipulator inside the TEM to assemble electrochemical cells with ionic liquid or solid state electrolytes, a capability that uses on-chip assembly of battery components on to TEM-compatible multi-electrode arrays, and a capability that uses a TEM-compatible sealed electrochemical cell that we developed for performing in-situ TEM using volatile battery electrolytes. These capabilities were used to understand lithiation mechanisms in nanoscale battery materials, including SnO 2 , Si, Ge, Al, ZnO, and MnO 2 . The modeling approaches used ab initio molecular dynamics to understand early stages of ethylene carbonate reduction on lithiated-graphite and lithium surfaces and constrained density functional theory to understand ethylene carbonate reduction on passivated electrode surfaces.

25 ENERGY STORAGE↗
DOE OSTI2013

Water and Carbon Dioxide Adsorption at Olivine Surfaces

Plane-wave density functional theory (DFT) calculations were performed to simulate water and carbon dioxide adsorption at the (010) surface of five olivine minerals, namely, forsterite (Mg2SiO4), calcio-olivine (Ca2SiO4), tephroite (Mn2SiO4), fayalite (Fe2SiO4), and Co-olivine (Co2SiO4). Adsorption energies per water molecule obtained from energy minimizations varied from -78 kJ mol-1 for fayalite to -128 kJ mol-1 for calcio-olivine at sub-monolayer coverage and became less exothermic as coverage increased. In contrast, carbon dioxide adsorption energies at sub-monolayer coverage ranged from -20 kJ mol-1 for fayalite to -59 kJ mol-1 for calcio-olivine. Therefore, the DFT calculations show a strong driving force for carbon dioxide displacement by water at the surface of all olivine minerals in a competitive adsorption scenario. Additionally, adsorption energies for both water and carbon dioxide were found to be more exothermic for the alkaline-earth (AE) olivines than for the transition-metal (TM) olivines and to not correlate with the solvation enthalpies of the corresponding divalent cations. However, a correlation was obtained with the charge of the surface divalent cation indicating that the more ionic character of the AE cations in the olivine structure relative to the TM cations leads to greater interactions with adsorbed water and carbon dioxide molecules at the surface and thus more exothermic adsorption energies for the AE olivines. For calcio-olivine, which exhibits the highest divalent cation charge of the five olivines, ab initio molecular dynamics simulations showed that this effect leads both water and carbon dioxide to react with the surface and form hydroxyl groups and a carbonate-like species, respectively.

ab initio molecular dynamics↗
NASA NTRS1984

Magnetic field line reconnection experiments. VI - Magnetic turbulence

Extensive statistical analysis of the vector components of fluctuating magnetic fields have been performed in a time dependent neutral magnetic sheet. Cross spectral analysis indicates a variety of wave numbers present for each frequency investigated. Comparison of Fourier components of the cross spectral function with dispersion surfaces in k space demonstrates the waves are large amplitude whistlers; this is verified by polarization analysis, which shows the random waves' magnetic fields to be right-hand circular. Ion acoustic and Langmuir turbulence are also observed along with bursts of microwave radiation. Measurements of the electron distribution function f(v, r, t) and its fluctuations in velocity space relate wave and particle activity.

Gekelman, W.↗
DOE OSTI2025

Tetracene Functionalized Si(111) Achieves Enhanced Solar-to-Chemical Energy Conversion via Molecular Acceptor States

The properties of semiconductor|liquid interfaces play a critical role in determining the efficiency of solar-to-hydrogen (STH) conversion. Here, we investigate how molecular functionalization of Si(111) and Si(111)|TiO 2 surfaces impacts photoelectrochemical (PEC) hydrogen production efficiency. We find that functionalization of ∼3% of the atop sites of Si(111) with either 9-anthracene (Anth) or 5-tetracene (Tet), with the remaining sites passivated by methyl groups, provides substrates with high electronic quality and low surface oxide densities, as determined by X-ray photoelectron spectroscopy (XPS) measurements. Surface photovoltage (SPV) spectroscopy shows that surfaces modified with Anth or Tet exhibit an increased photovoltage, with Tet-functionalized surfaces yielding an additional 192 meV relative to methyl-terminated Si(111), indicating improved charge separation for Si-Tet. Further improvement in onset potential was achieved by replacing a nitrogen-containing TiO 2 atomic layer deposition (ALD) precursor (TDMAT) with a precursor lacking nitrogen (TTIP), which eliminates the parasitic defect band in the TiO 2 overlayer (p-Si(111)-Tet|TTIP-TiO 2 |Pt: V OC = +0.283 ± 0.041 V vs RHE). Density functional theory (DFT) analysis demonstrates that compared with Anth-modified Si(111), the Tet-modified surface exhibits more hybridized Si(111)-Tet states closer to the silicon band edges. Mercury contact current–voltage (I–V, dark) measurements quantified the relative interfacial density of states of Si-Tet, Si-Anth and Si-Me surfaces─revealing that the interfacial state density was highest for Si-Tet. This suggests that such hybridized interfaces serve to capture better photoexcited charge, which enables facile electron transfer to molecular acceptors in solution. Altogether, the data indicate that beneficial hybrid molecular LUMO surface states interacting with the Si conduction band edge results in improved hydrogen evolution (HER) performance for p-Si devices.

Group theory↗
NASA NTRS1980

Orthogonality of spherical harmonic coefficients

Orthogonality relations are obtained for the spherical harmonic coefficients of functions defined on the surface of a sphere. Following a brief discussion of the orthogonality of Fourier series coefficients, consideration is given to the values averaged over all orientations of the coordinate system of the spherical harmonic coefficients of a function defined on the surface of a sphere that can be expressed in terms of Legendre polynomials for the special case where the function is the sum of two delta functions located at two different points on the sphere, and for the case of an essentially arbitrary function. It is noted that the orthogonality relations derived have found applications in statistical studies of the geomagnetic field.

Mcleod, M. G.↗