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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 559 records · Page 31
All sourcesNASA NTRSDOE OSTI
NASA NTRS1999

The ISO View of Star Forming Galaxies

ISO studies of normal galaxies in the local Universe have revealed basic new properties whose significant implications for the star formation process and cosmology are only starting to be understood. This review will touch on the general results of a statistical nature, and provide a quick summary of the profusion of exciting results on individual objects. In the mid-infrared, PHT-S has established that the spectra of star forming galaxies between 6 and-13microns are dominated by the Aromatic Features in Emission (AFE), and show little variation as a function of the heating intensity. The Carriers of the AFE (CAFE) are thus a universal component of dust with standard properties, and contribute between 10 and 25% of the total dust luminosity. In addition to AFE, the spectra show a low-level continuum detectable at wavelengths longer than 3.5microns whose origin is still under investigation. The mid-infrared colors formed as the ratio of flux densities in the 6.75micron and the 15micron bands of ISO-CAM remain essentially constant and near unity for quiescent and mildly active galaxies. As dust heating increases further, the 15micron flux increases steeply compared to 6.75microns, indicating that dust heated to 100K<T<200K becomes a significant component. Such hot dust is presumably located within or just outside HII regions. At the other end of the spectrum, photometry at 120-200microns using ISO-PHOT is starting to constrain the distribution of dust temperatures at the low end of the temperature scale. From LWS data, the far-infrared fine-structure lines of [CII] and [OI], which provide most of the cooling for warm atomic gas, show variations that have remained controversial in their interpretation. In particular, as the galaxy become more active in star formation, its [CII] flux weakens relative to total dust emission while the [OI] does not. This behavior has attracted much interest because it extrapolates to the most active galaxies, making them weaker in [CII] than previously expected. Several explanations for the effect have been advanced, and will be discussed in this review. Spectroscopy with SWS has measured molecular hydrogen in galaxies, providing a powerful handle on the warm molecular gas content. SWS and CAM-CVF studies targeting ionic fine-structure lines have demonstrated their value as diagnostics of the radiation field.

Helou, George↗
NASA NTRS2016

The Habitability of Proxima Centauri b II. Possible Climates and Observability

Radial velocity monitoring has found the signature of a M sin i = 1.3 M(sub ⨁) planet located within the habitable zone (HZ) of Proxima Centauri. Despite a hotter past and an active host star, the planet Proxima b could have retained enough volatiles to sustain surface habitability. Here we use a 3D Global Climate Model (GCM) to simulate the atmosphere and water cycle of Proxima b for its two likely rotation modes (1:1 and 3:2 spin-orbit resonances), while varying the unconstrained surface water inventory and atmospheric greenhouse effect. Any low-obliquity, low-eccentricity planet within the HZ of its star should be in one of the climate regimes discussed here. We find that a broad range of atmospheric compositions allow surface liquid water. On a tidally locked planet with sufficient surface water inventory, liquid water is always present, at least in the substellar region. With a non-synchronous rotation, this requires a minimum greenhouse warming (~10 mbar of CO2 and 1 bar of N2). If the planet is dryer, ~0.5 bar or 1.5 bars of CO2 (for asynchronous or synchronous rotation, respectively) suffice to prevent the trapping of any arbitrary, small water inventory into polar or nightside ice caps. We produce reflection and emission spectra and phase curves for the simulated climates. We find that atmospheric characterization will be possible via direct imaging with forthcoming large telescopes. The angular separation of 7 λ/D at 1 μm (with the E-ELT) and a contrast of ~10(exp -7) will enable high-resolution spectroscopy and the search for molecular signatures, including H2O, O2, and CO2. The observation of thermal phase curves can be attempted with the James Webb Space Telescope, thanks to a contrast of 2 × 10(exp -5) at 10 μm. Proxima b will also be an exceptional target for future IR interferometers. Within a decade it will be possible to image Proxima b and possibly determine whether the surface of this exoplanet is habitable.

Proxima Cen↗
DOE OSTI2022

Machine Learning Models for Binary Molecular Classification using VUV Absorption Spectra

Machine learning methods were combined with differential absorption spectroscopy measurements in the vacuum-ultraviolet region (5.167 – 9.920 eV) in order to develop predictive capabilities for inferring molecular structure from the spectra. Several types of species were analyzed and, for modeling purposes, were defined using a single classification: (1) alkane, (2) conjugation with oxygen (e.g. diacetyl, ethyl vinyl ether), (3) non-conjugated alkene (e.g. 1-butene, 1,4-cyclohexadiene), (4) oxygen-containing (e.g. 1-butanol, tetrahydrofuran), or (5) cyclic (e.g. cyclopentane, cyclohexanone). The latter molecular classification excluded cyclic ethers. Several modeling methods were employed in the analysis of 102 absorption spectra, 24 of which were measured for the first time. The primary objective was to identify suitable methods that enable accurate predictions of molecular structure classifications with minimized statistical uncertainties. Rather than identifying a single, unifying method to reliably predict molecular structure contributions to VUV absorption spectra, coordination is required among a particular method, the type of molecular structure detail (e.g. conjugation), and absorption region of interest. The latter is accomplished using a binning approach, wherein absorption regions of ~0.5 eV were utilized rather than the entire ~4.8 eV range. Photon energy binning enabled analysis of region-specific predictions of accuracy, precision, and recall. The outcome from the binning approach is that, rather than utilizing the entire spectrum, optimal determination of molecular structure using machine learning methods depends on the absorption region. Furthermore, the present work provides separate machine learning models for each molecular classification, which enables the identification of multi-functional species relevant to atmospheric chemistry and combustion chemistry, where isomer-resolved speciation is critical to understanding complex reaction networks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

The 2 micron spectrum of NGC 6240 - Evidence for more than a starburst

The exceptionally luminous interacting galaxy NGC 6240 has been studied with infrared spectroscopy and photometry. Emission lines of molecular hydrogen and the Paschen-alpha line of ionized hydrogen have been detected. Broad-band 10 micron and 20 micron emission has also been observed. Combined with previous optical spectroscopy and results from IRAS, the observations show that NGC 6240 cannot be explained along the lines of a superstarburst of massive stars such as seen in M82. It may be more easily understood in terms of an active nucleus similar to Seyfert galaxies.

Depoy, D. L.↗
DOE OSTI2020

Laser-Plasma Spectroscopy of Hydroxyl with Applications

This article discusses laser-induced laboratory-air plasma measurements and analysis of hydroxyl (OH) ultraviolet spectra. The computations of the OH spectra utilize line strength data that were developed previously and that are now communicated for the first time. The line strengths have been utilized extensively in interpretation of recorded molecular emission spectra and have been well-tested in laser-induced fluorescence applications for the purpose of temperature inferences from recorded data. Moreover, new experiments with Q-switched laser pulses illustrate occurrence of molecular recombination spectra for time delays of the order of several dozen of microseconds after plasma initiation. The OH signals occur due to the natural humidity in laboratory air. Centrifugal stretching of the Franck-Condon factors and r-centroids are included in the process of determining the line strengths that are communicated as a Supplementary File. Laser spectroscopy applications of detailed OH computations include laser-induced plasma and combustion analyses, to name but two applications. This work also includes literature references that address various diagnosis applications.

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

In Situ Spectroscopic Monitoring of MSR Molten Salt and Off-Gas Systems

A significant challenge that must be overcome before commercialization of molten salt reactors is tracking special nuclear material (SNM) through the reactor and subsystems such as fuel chemical processing and off-gas systems. In recent years, several approaches have been explored to track SNM, fission products, and corrosion products in these different subsystems. One such approach is to employ laser and optical spectroscopy to measure the atomic and molecular signals of MSR salts. The advantages of these approaches are that they typically are non-intrusive and offer the capability of process monitoring while still providing low uncertainties. At the Idaho National Laboratory, spectroscopy approaches such as laser-induced breakdown spectroscopy (LIBS) and ultraviolet-visible (UV-Vis) spectroscopy have been utilized to investigate molten salts in an aerosol (LiCl, KCl, RbCl2, NdCl3, and PrCl3) and vapor phases (MgCl5, NdCl5, and ZrCl4) with success. Testing to date has yielded qualitative information on all the above species and quantitative data and analytical figures of merit for species in the vapor phases. These findings, including results from ongoing testing, as well as the experimental conditions and potential applications will be presented.

98 - NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL↗
DOE OSTI2021

Understanding Spin Coherence in Polyoxometalate-Based Molecular Qubits

This research advances the understanding of spin decoherence mechanisms and addresses the grand challenges in quantum information science of generating and stabilizing quantum states that may be manipulated with single-atom precision. It is accomplished using unique capabilities developed at PNNL for ion soft landing and spatially resolved vibrational spectroscopy of well-defined supported molecular qubit (MQ) arrays. It addresses knowledge gaps impeding the development of MQ-based quantum devices by answering two scientific questions: 1) Can we minimize spin-lattice relaxation rates by tuning the substrate-MQ interface? 2) What is the optimum number of spin centers that enables sufficient coherent signal generation prior to decoherence through inter-MQ and MQ-support interactions? The objective is to develop predictive design principles for prolonging spin coherence lifetimes in arrays of optically-addressable MQs for quantum computing applications.

97 MATHEMATICS AND COMPUTING↗
NASA NTRS1985

Far-infrared spectroscopy of galaxies - The 158 micron C(+) line and the energy balance of molecular clouds

Observations of the 158 microns fine-structure line of C(+) toward the nuclei of six gas-rich galaxies are presented. The observations are compared with observations of the CO J = 1-0 and H I 21 cm lines, observations of far-IR continuum emission, and observations of forbidden C II emission with the Galaxy. The forbidden C II line comes from dense, warm gas in UV-illuminated photodissociation regions at the surfaces of molecular clouds. This line is probably optically thin in all but the brightest of galactic sources. The variation of forbidden C II brightness from source to source and its ratio to the integrated infrared continuum intensity agree well with the theoretical prediction that UV absorption by dust controls the C(+) column density. The forbidden C II line is a tracer of molecular clouds, especially those near intense sources of UV radiation.

Crawford, M. K.↗
DOE OSTI2021

Nanoparticle-Induced Disorder at Complex Liquid–Liquid Interfaces: Effects of Curvature and Compositional Synergy on Functional Surfaces

The self-assembly of surfactant monolayers at interfaces plays a sweeping role in tasks ranging from household cleaning to the regulation of the respiratory system. The synergy between different nanoscale species at an interface can yield assemblies with exceptional properties, which enhance or modulate their function. However, understanding the mechanisms underlying coassembly, as well as the effects of intermolecular interactions at an interface, remains an emerging and challenging field of study. Herein, we study the interactions of gold nanoparticles striped with hydrophobic and hydrophilic ligands with phospholipids at a liquid–liquid interface and the resulting surface-bound complexes. We show that these nanoparticles, which are themselves minimally surface active, have a direct concentration-dependent effect on the rapid reduction of tension for assembling phospholipids at the interface, implying molecular coassembly. Through the use of sum frequency generation vibrational spectroscopy, we reveal that nanoparticles impart structural disorder to the lipid molecular layers, which is related to the increased volumes that amphiphiles can sample at the curved surface of a particle. The results strongly suggest that hydrophobic and electrostatic attractions imparted by nanoparticle functionalization drive lipid–nanoparticle complex assembly at the interface, which synergistically aids lipid adsorption even when lipids and nanoparticles approach the interface from opposite phases. The use of tensiometric and spectroscopic analyses reveals a physical picture of the system at the nanoscale, allowing for a quantitative analysis of the intermolecular behavior that can be extended to other systems.

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

Experimental determination of the temperature-dependent Van Hove function in a Zr 80 Pt 20 liquid

Even though the viscosity is one of the most fundamental properties of liquids, the connection with the atomic structure of the liquid has proven elusive. By combining inelastic neutron scattering with the electrostatic levitation technique, the time-dependent pair-distribution function (i.e., the Van Hove function) has been determined for liquid Zr 80 Pt 20 . We show that the decay time of the first peak of the Van Hove function is directly related to the Maxwell relaxation time of the liquid, which is proportional to the shear viscosity. This result demonstrates that the local dynamics for increasing or decreasing the coordination number of local clusters by one determines the viscosity at high temperature, supporting earlier predictions from molecular dynamics simulations.

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

Dynamic Copper Site Redispersion through Atom Trapping in Zeolite Defects

Single-site copper-based catalysts have shown remarkable activity and selectivity for a variety of reactions. However, deactivation by sintering in high-temperature reducing environments remains a challenge and often limits their use due to irreversible structural changes to the catalyst. Here, we report zeolite-based copper catalysts in which copper oxide agglomerates formed after reaction can be repeatedly redispersed back to single sites using an oxidative treatment in air at 550 °C. Under different environments, single-site copper in Cu–Zn–Y/deAlBeta undergoes dynamic changes in structure and oxidation state that can be tuned to promote the formation of key active sites while minimizing deactivation through Cu sintering. For example, single-site Cu 2+ reduces to Cu 1+ after catalyst pretreatment (270 °C, 101 kPa H 2 ) and further to Cu0 nanoparticles under reaction conditions (270–350 °C, 7 kPa EtOH, 94 kPa H 2 ) or accelerated aging (400–450 °C, 101 kPa H 2 ). After regeneration at 550 °C in air, agglomerated CuO was dispersed back to single sites in the presence and absence of Zn and Y, which was verified by imaging, in situ spectroscopy, and catalytic rate measurements. Ab initio molecular dynamics simulations show that solvation of CuO monomers by water facilitates their transport through the zeolite pore, and condensation of the CuO monomer with a fully protonated silanol nest entraps copper and reforms the single-site structure. Importantly, the capability of silanol nests to trap and stabilize copper single sites under oxidizing conditions could extend the use of single-site copper catalysts to a wider variety of reactions and allows for a simple regeneration strategy for copper single-site catalysts.

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

Ion Pairing and Molecular Orientation at Liquid/Liquid Interfaces: Self-Assembly and Function

We report that molecular orientation plays a pivotal role in defining the functionality and chemistry of interfaces, yet accurate measurements probing this important feature are few, due, in part, to technical and analytical limitations in extracting information from molecular monolayers. For example, buried liquid/liquid interfaces, where a complex and poorly understood balance of inter- and intramolecular interactions impart structural constraints that facilitate the formation of supramolecular assemblies capable of new functions, are difficult to probe experimentally. Here, we use vibrational sum-frequency generation spectroscopy, numerical polarization analysis, and atomistic molecular dynamics simulations to probe molecular orientations at buried oil/aqueous interfaces decorated with amphiphilic oligomers. We show that the orientation of self-assembled oligomers changes upon the addition of salts in the aqueous phase. The evolution of these structures can be described by competitive ion effects in the aqueous phase altering the orientations of the tails extending into the oil phase. These specific anionic effects occur via interfacial ion pairing and associated changes in interfacial solvation and hydrogen-bonding networks. These findings provide more quantitative insight into orientational changes encountered during self-assembly and pave the way for the design of functional interfaces for chemical separations, neuromorphic computing applications, and related biomimetic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

Electronic Transport through Self Assembled Thiol Molecules: Effect of Monolayer Order, Dynamics and Temperature

We present the charge transport and tunneling conductance of self assembled organic thiol molecules and discuss the influence of order and dynamics in the monolayer on the transport behavior and the effect of temperature. Conjugated thiol molecular wires and organometals such as terpyridine metal complexes provide a new platform for molecular electronic devices and we study their self assembly on Au(111) substrates by the scanning tunneling microscope. Determining the organization of the molecule and the ability to control the nature of its interface with the substrate is important for reliable performance of the molecular electronic devices. By concurrent scanning tunneling microscopy and spectroscopy studies on SAMs formed from oligo (phenelyne ethynelyne) monolayers with and without molecular order, we show that packing and order determine the response of a self assembled monolayer (SAM) to competing interactions. Molecular resolution STM imaging in vacuum shows that the OPES adopt an imcommensurate SAM structure on Au(111) with a rectangular unit cell. Tunneling spectroscopic measurements were performed on the SAM as a function of junction resistance. STS results show that the I-Vs are non linear and asymmetric due to the inherent asymmetry in the molecular structure, with larger currents at negative sample biases. The asymmetry increases with increasing junction resistance due to the asymmetry in the coupling to the leads. This is brought out clearly in the differential conductance, which also shows a gap at the Fermi level. We also studied the effect of order and dynamics in the monolayer on the charge transport and found that competing forces between the electric field, intermolecular interactions, tip-molecule physisorption and substrate-molecule chemisorption impact the transport measurements and its reliability and that the presence of molecular order is very important for reproducible transport measurements. Thus while developing new electronic platforms based on molecules, it is important to have a good control of the molecule-substrate interface, for the devices to perform reliably. While such a control would minimize fluctuations and dynamics in the ensemble, the real challenge is to develop device architectures that are tolerant to fluctuations, since they cannot be totally eliminated in these low dimensional soft systems. Results of temperature dependent STS measurements will also be discussed.

Dholakia, Geetha↗
DOE OSTI2024

A comprehensive study on three typical photoacid generators using photoelectron spectroscopy and ab initio calculations

Conducting a comprehensive molecular-level evaluation of a photoacid generator (PAG) and its subsequent impact on lithography performance can facilitate the rational design of a promising 193 nm photoresist tailored to specific requirements. In this study, we integrated spectroscopy and computational techniques to meticulously investigate the pivotal factors of three prototypical PAG anions, p-toluenesulfonate (pTS - ), 2-(trifluoromethyl)benzene-1-sulfonate (TFMBS - ), and triflate (TF - ), in the lithography process. Our findings reveal a significant redshift in the absorption spectra caused by specific PAG anions, attributed to their involvement in electronic transition processes, thereby enhancing the transparency of the standard PAG cation, triphenylsulfonium (TPS + ), particularly at ~193 nm. Furthermore, the electronic stability of PAG anions can be enhanced by solvent effects with varying degrees of strength. Here we observed the lowest vertical detachment energy of 6.6 eV of pTS - in PGMEA solution based on the polarizable continuum model, which prevents anion loss at 193 nm lithography. In addition, our findings indicate gas-phase proton affinity values of 316.4 kcal/mol for pTS - , 308.1 kcal/mol for TFMBS - , and 303.2 kcal/mol for TF - , which suggest the increasing acidity strength, yet even the weakest acid pTS - is still stronger than strong acid HBr. The photolysis of TPS + -based PAG, TPS + ·pTS - , generated an excited state leading to homolysis bond cleavage with the lowest reaction energy of 83 kcal/mol. Overall, the PAG anion pTS - displayed moderate acidity, possessed the lowest photolysis reaction energy, and demonstrated an appropriate redshift. These properties collectively render it a promising candidate for an effective acid producer.

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

Ultrafast electronic relaxation pathways of the molecular photoswitch quadricyclane

Abstract The light-induced ultrafast switching between molecular isomers norbornadiene and quadricyclane can reversibly store and release a substantial amount of chemical energy. Prior work observed signatures of ultrafast molecular dynamics in both isomers upon ultraviolet excitation but could not follow the electronic relaxation all the way back to the ground state experimentally. Here we study the electronic relaxation of quadricyclane after exciting in the ultraviolet (201 nanometres) using time-resolved gas-phase extreme ultraviolet photoelectron spectroscopy combined with non-adiabatic molecular dynamics simulations. We identify two competing pathways by which electronically excited quadricyclane molecules relax to the electronic ground state. The fast pathway (<100 femtoseconds) is distinguished by effective coupling to valence electronic states, while the slow pathway involves initial motions across Rydberg states and takes several hundred femtoseconds. Both pathways facilitate interconversion between the two isomers, albeit on different timescales, and we predict that the branching ratio of norbornadiene/quadricyclane products immediately after returning to the electronic ground state is approximately 3:2.

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

Ab Initio Molecular Dynamics Simulation of Divalent Metal Cation Incorporation in Calcite: Implications for Interpreting X-ray Absorption Spectroscopy Data

Calcite (CaCO 3 ) is a ubiquitous mineral with the ability to accommodate a wide range of impurities. Determination of the coordination environment and incorporation modes of impurities in calcite has historically relied primarily on the interpretation of extended X-ray absorption fine structure (EXAFS) spectroscopy. However, lack of standards combined with the large number of degrees of freedom involved in shell-by-shell fits have made the interpretation of EXAFS spectra challenging. As such, in this work, ab initio molecular dynamics (AIMD) simulations were performed to investigate the incorporation of seven divalent metal cation impurities, namely, Ba 2+ , Pb 2+ , Sr 2+ , Cd 2+ , Mn 2+ , Co 2+ , and Zn 2+ , in calcite. These cations span a wide range of sizes: 30.7 to –22.8% change in ionic radius with respect to Ca 2+ . The atomic trajectories were then used to compute EXAFS spectra for direct comparison with published experimental spectra. The simulations confirmed that all seven metal cations incorporate in calcite via substitution in the calcium site. The AIMD–EXAFS approach allowed for overcoming limitations of the shell-by-shell fitting approach, such as the difficulties in resolving weak backscatterers beyond the first coordination shell. As a result, the AIMD–EXAFS approach was able to provide a detailed and comprehensive characterization of the structural relaxation around divalent metal cation impurities in calcite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗