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At least 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
NASA NTRS1985

Is the Kolmogoroff model applicable to large-scale turbulence?

In view of the present discussion, the Heisenberg-Kolmogoroff (HK) model of turbulence that is often used for turbulent phenomena on all scales is actually valid for a turbulent spectrum wavelength band typically much smaller than the size of the system, and cannot describe phenomena at large scales in astrophysical systems. The results of mixing length theory cannot be accommodated within the HK model's framework without the adoption of an unreasonable coupling constant. It is also noted that the use of the observed velocity-size relationship in molecular clouds with turbulent velocity values of about l to the 1/2-power, within the HK model, gives rise to a growth rate that does not correspond to any known physical processes suspected of operating in molecular clouds.

Canuto, V. M.↗
NASA NTRS1993

Molecular processes in comets

A major effort was expended in developing procedures for calculating by quantum-mechanical methods the cross sections for the photodissociation of the hydroxyl radical OH. The molecule OH is the primary dissociation product of water and observations of OH when combined with a determination of the lifetime of OH in the solar radiation field can be used to calculate the rate of release of water from comets. There are many possible photodissociation channels whose efficiency depends upon the details of the spectrum of the radiation. We have calculated the potential energy curves of all the states of OH that can be reached by electric dipole absorption from the ground X(exp 2)(Pi) state by photons with energies up to about 12 eV.

Dalgarno, A.↗
DOE OSTI2020

Ab initio molecular dynamics simulation of Nd3+ incorporation in calcite

Trivalent rare-earth elements (REEs) readily incorporate in Ca-bearing minerals such as calcite (CaCO3), a phenomenon with important implications for the use of REEs as biogeochemical tracers as well as for environmental remediation. Despite substantial efforts, determining the incorporation modes of trivalent REEs in calcite has remained challenging due to their presence in multiple coordination environments. This is particularly problematic for the interpretation of extended X-ray absorption fine structure (EXAFS) spectroscopy. In this work, ab initio molecular dynamics (AIMD) simulations of Nd3+ incorporated in calcite were performed to resolve its incorporation modes. Nd3+ and Ca2+ have very similar ionic radii but the additional positive charge requires a charge compensation scheme (CCS). Five CCSs were considered in AIMD simulations, and the resulting atomic trajectories were then used to compute EXAFS spectra for direct fitting to a published experimental spectrum. The results of the fits indicated that Nd3+ incorporates at the Ca2+ site in calcite in a mixture of six- and seven-fold coordination environments and through three main incorporation modes: associated with a protonated nearest-neighbor Ca2+ vacancy, incorporated as NdOH2+, and charge compensated by a remote species (on the spatial scale probed by EXAFS). The incorporation of Nd3+ in calcite via multiple modes was consistent with previous work, but the AIMD-EXAFS approach allowed for resolving the nature, proportion, and structure of the different coordination environments.

Kerisit, Sebastien N.↗
DOE OSTI2026

Deciphering the Solvation Structure of Aqueous ZnCl 2 Solutions from X-ray Absorption Spectra Using the Interpretable Graph Neural Network

Machine learning (ML) provides powerful pathways for predicting spectroscopic observables from atomic structures, but its broader impact depends on making model predictions interpretable in terms of physical and chemical principles. Here, we introduce a physics-guided graph neural network (GNN) model that predicts Zn K-edge X-ray spectroscopy (XAS) spectra of aqueous ZnCl 2 solutions. Training data are generated from ab initio XAS calculations on molecular dynamics snapshots obtained using a machine learning interatomic potential. The GNN reproduces experimental spectra across concentrations from dilute (<0.1 m) to highly concentrated (30 m, “water-in-salt”) regimes and scales efficiently to large, disordered liquid systems beyond the reach of conventional ab initio approaches. Gradient-based attribution analysis reveals that the model learns physically meaningful structure-spectrum relationships. Ligand-specific attributions reflect orbital hybridization patterns and the origin of the excitations derived from the density functional theory. Bond-length attributions recover spectral shifts consistent with multiple-scattering theory. Finally, this work bridges data-driven prediction with electronic-structure theory, establishing a general paradigm for interpretable ML that links atomic structure, electronic structure, and spectroscopic observables.

25 ENERGY STORAGE↗
DOE OSTI2024

Uncovering the binding nature of thiocyanate in contact ion pairs with lithium ions

Ion pair formation is a fundamental molecular process that occurs in a wide variety of systems, including electrolytes, biological systems, and materials. In solution, the thiocyanate (SCN–) anion interacts with cations to form contact ion pairs (CIPs). Due to its ambidentate nature, thiocyanate can bind through either its sulfur or nitrogen atoms, depending on the solvent. This study focuses on the binding nature of thiocyanate with lithium ions as a function of the solvents using FTIR, 2D infrared spectroscopy (2DIR) spectroscopies, and theoretical calculations. The study reveals that the SCN– binding mode (S or N end) in CIPs can be identified through 2DIR spectroscopy but not by linear IR spectroscopy. Linear IR spectroscopy shows that the CN stretch frequencies are too close to one another to separate N- and S-bound CIPs. Moreover, the IR spectrum shows that the S–C stretch presents different frequencies for the salt in different solvents, but it is related to the anion speciation rather than to its binding mode. A similar trend is observed for the anion bend. 2DIR spectra show different dynamics for N-bound and S-bound thiocyanate. In particular, the frequency–frequency correlation function (FFCF) dynamics extracted from the 2DIR spectra have a single picosecond exponential decay for N-bound thiocyanate and a biexponential decay for S-bound thiocyanate, consistent with the binding mode of the anion. Lastly, it is also observed that the binding mode also affects the line shape parameters, probably due to the different molecular mechanisms of the FFCF for N- and S-bound CIPs.

25 ENERGY STORAGE↗
DOE OSTI2025

Ligand efficacy shifts a nuclear receptor conformational ensemble between transcriptionally active and repressive states

Abstract Nuclear receptors (NRs) are thought to dynamically alternate between transcriptionally active and repressive conformations, which are stabilized upon ligand binding. Most NR ligand series exhibit limited bias, primarily consisting of transcriptionally active agonists or neutral antagonists, but not repressive inverse agonists—a limitation that restricts understanding of the functional NR conformational ensemble. Here, we report a NR ligand series for peroxisome proliferator-activated receptor gamma (PPARγ) that spans a pharmacological spectrum from repression (inverse agonism) to activation (agonism) where subtle structural modifications switch compound activity. While crystal structures provide snapshots of the fully repressive state, NMR spectroscopy and conformation-activity relationship analysis reveals that compounds within the series shift the PPARγ conformational ensemble between transcriptionally active and repressive conformations that are natively populated in the apo/ligand-free ensemble. Our findings reveal a molecular framework for minimal chemical modifications that enhance PPARγ inverse agonism and elucidate their influence on the dynamic PPARγ conformational ensemble.

Science & Technology - Other Topics↗
DOE OSTI2023

Molecular hydrodynamic theory of the velocity autocorrelation function

The velocity autocorrelation function (VACF) encapsulates extensive information about a fluid’s molecular-structural and hydrodynamic properties. We address the following fundamental question: How well can a purely hydrodynamic description recover the molecular features of a fluid as exhibited by the VACF? To this end, we formulate a bona fide hydrodynamic theory of the tagged-particle VACF for simple fluids. Our approach is distinguished from previous efforts in two key ways: collective hydrodynamic modes and tagged-particle self-motion are modeled by linear hydrodynamic equations; the fluid’s spatial velocity power spectrum is identified as a necessary initial condition for the momentum current correlation. This formulation leads to a natural physical interpretation of the VACF as a superposition of products of quasinormal hydrodynamic modes weighted commensurately with the spatial velocity power spectrum, the latter of which appears to physically bridge continuum hydrodynamical behavior and discrete-particle kinetics. The methodology yields VACF calculations quantitatively on par with existing approaches for liquid noble gases and alkali metals. Furthermore, we obtain a new, hydrodynamic form of the self-intermediate scattering function whose description has been extended to low densities where the Schmidt number is of order unity; various calculations are performed for gaseous and supercritical argon to support the general validity of the theory. Excellent quantitative agreement is obtained with recent MD calculations for a dense supercritical Lennard-Jones fluid.

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

A Starfish Preplanetary Nebula: IRAS 19024+0044

Using the Hubble Space Telescope, we have imaged the OH/IR star IRAS 19024+0044 (I19024) at 0.6, 0.8, 1.1, and 1.6 micrometers, as part of our surveys of candidate preplanetary nebulae. The images show a multipolar nebula of size approximately equal to 3.'7 2.'3, with at least six elongated lobes emanating from the center of the nebula. Two of the lobes show limb-brightened tips having point-symmetric structure with respect to the expected location of the central star. The central region shows two dark bands southwest and northeast of a central shallow maximum that may be either two inclined dusty toroidal structures or the dense parts of a single wide, inhomogeneous, toroid. Avery faint, surface brightness-limited, diffuse halo surrounds the lobes. Long-slit/echelle optical spectroscopy obtained at the Mount Palomar and Keck observatories shows a spatially compact source of H(alpha) emission; the H(alpha) line shows a strong, narrow, central core with very broad (+/-1000 km/sec), weak wings, and a narrower blueshifted absorption feature signifying the presence of an approximately 100 km/sec(exp -1) outflow. The spectrum is characterized by a strong, relatively featureless, continuum and lacks the strong forbidden emission lines characteristic of planetary nebulae, confirming that IRAS 19024 is a preplanetary nebula; the spectral type for the central star, although uncertain, is most likely early G. Interferometric observations of the CO J = 1 -0 line emission with the Owens Valley Radio Interferometer show a marginally resolved molecular envelope (size 5.'5 x 4.'4) with an expansion velocity of 13 km/sec (exp -1), resulting from the asymptotic giant branch (AGB) progenitor's dense, slow wind. We derive a kinematic distance of 3.5 kpc to I19024, based on its radial velocity. The bolometric flux is 7:3 x 10(exp -9) erg s(exp -1) cm(exp -2), and the luminosity 2850 L. The relatively low luminosity of I19024, in comparison with stellar evolutionary models, indicates that the initial mass of its central star was approximately 1-1.5 solar mass. The lobes, which appear to be hollow structures with dense walls, have a total mass greater than or equal to about 0.02 solar mass. The lobes, which appear to be hollow structures with dense walls, have a total mass greater than or equal to about 0.02 solar mass. The dusty tori in the center have masses of a few times 10(exp -3) solar mass. The faint halo has a power-law radial surface brightness profile with an exponent of about -3 and most likely represents the remnant spherical circumstellar envelope formed as a result of constant mass loss during the AGB expansion age of less than or approximately equal to 2870 yr, giving a mass-loss rate of greater than or approximately equal to 10(exp -5) solar mass yr (exp -1), The far-infrared fluxes of I19024 indicate the presence of a large mass of cool dust in the nebula, from a simple model we infer the presence of 'cool' (109 K) and 'warm' (280 K) components of dust mass 5.7 x 10(exp -4) and 1.5 x 10(exp -7) solar mass. We discuss our results for I19024 in the light of past and current ideas for the dramatic transformation of the morphology and kinematics of mass-ejecta as AGB stars evolve into planetary nebulae.

circumstellar matter↗
DOE OSTI2023

A First Principles Approach to Spectral Phonon Transport in Heterostructures

Understanding thermal transport across interfaces which give rise to a thermal resistance (also known as Kapitza resistance) is a critical issue affecting the development of nanotechnologies. Much modern and emergent nanotechnology consist of adjacent materials, and phonon mediated heat transfer governs thermal behavior across internal interfaces in these devices. The physics of thermal transport in solids are governed both by phenomena occurring at the atomic scale and interactions with the material's microstructure. The forecasting of fundamental quantities such as temperature, heat flux and thermal conductivity typically employs the semi-classical Boltzmann transport equation to predict the macroscopic behavior of materials in terms of the microscopic dynamics of its heat carriers. Kapitza resistance was first discovered in liquid helium experiments and has led to a fundamental research thrust in micro and nano-scale heat transport, the behavior of thermal carriers across internal interfaces. Thermal interfacial resistance (TIR) is a widely studied phenomenon, first engaged by Swartz and Pohl through their development of the acoustic and diffuse mismatch methods, then continued through myriad efforts with varying methods and approaches in an attempt to resolve carrier behavior at thermal interfaces. Many of the fundamental approaches to TIR have been at the nanoscale, and research is conducted with molecular dynamics (MD) and density functional theory (DFT) methods. The limitations of these methods is system size; atomistic methods tend to be limited to system sizes of 100,000 atoms or less. Larger length-scale methods have also been pursued, based on the principles of acoustic or diffuse mismatch, but not all include simulation of TIR using a full phonon band spectrum, or temperature dependent methods. Our approach to enabling phonon transport in layered materials draws upon our previous work of demonstrating spectrally coupled phonon transport in homogeneous and heterogeneous materials. We use a semi-analytical approach in which the Bose-Einstein (B-E) statistics set the strength of the phonon radiance in a frequency group, but the B-E statistics are informed with information from the transport system. The B-E statistics in a single frequency group feels the influence of all the groups through the spatial temperature. We also include a new field term which is an indicator of the amount of non-equilibrium behavior of the phonon spectrum---this is added to the phonon source term in all groups to ensure closure and conservation of energy, as the phonon groups in the transport system and the analytical systems are coupled. This work builds upon our previous approach by adding a phonon coupling term at an internal interface, using the principles of the DMM through transmission and reflection coefficients. In this work, the coefficients are determined through computing a common temperature at the interface, influenced by the phonon band structure of both materials, in effect, providing mixing between the two material systems and using the common temperature to set the strength of the phonon radiance at the boundaries on either side of the interface. Our approach uses material properties computed along various crystallographic orientations, and while some isotropy is built into the interface condition, the material properties weight the phonon distributions in the proper crystalline direction. Greater resolution of phonon behavior in proximity to an interface, and more accurate predictions of TIR are obtained. While it is true the assumption of diffuse mismatch can yield inconsistent results compared to experiment especially at low temperatures, this work focuses on room temperature and beyond effects, for future applications in nuclear fuel, or thermoelectric devices; a modified mismatch approach may be feasible if applied properly. Additionally, our methods focus on bridging mesoscale to engineering scale

36 MATERIALS SCIENCE↗
NASA NTRS1985

A new emission feature in IRAS spectra and the polycyclic aromatic hydrocarbon spectrum

IRAS spectra of those sources which show strong 7.7 and 11.3 micron emission features also show a plateau of emission extending from 11.3 to about 13.0 microns. Like the 11.3 micron feature, this new feature is attributed to the CH out-of-plane bending mode in polycyclic aromatic hydrocarbons (PAHs). Its discovery reinforces the identification of the 'unidentified infrared emission features' as emission from PAHs. The wavelength of this new feature suggests that interstellar PAHs are not as partially hydrogenated as hitherto thought. It also constrains their molecular structure.

Cohen, M.↗
NASA NTRS1989

A high-resolution atlas of the infrared spectrum of the sun and the earth atmosphere from space. A compilation of ATMOS spectra of the region from 650 to 4800 cm-1 (2.3 to 16 microns). Volume 2: Stratosphere and mesosphere, 650 to 3350 cm-1

During the period April 29 to May 2, 1985, the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment was operated for the first time, as part of the Spacelab-3 payload of the shuttle Challenger. The principal purpose of this experiment was to study the distributions of the atmosphere's minor and trace molecular constituents. The instrument, a modified Michelson interferometer covering the frequency range from 600 to 5000/cm-1 at a spectral resolution of 0.01/cm-1, recorded infrared absorption spectra of the sun and of the earth's atmosphere at times close to entry into and exit from occultation by the earth's limb. Spectra were obtained that are free from absorptions due to constituents of the atmosphere (i.e., they are pure solar spectra), as well as spectra of the atmosphere itself, covering line-of-sight tangent altitudes that span the range from the lower thermosphere to the bottom of the troposphere. This atlas presents a compilation of these spectra arranged in a hardcopy format suitable for quick-look reference purposes. Volume 2 covers the stratosphere and mesosphere (i.e., tangent altitudes from 20 to 80 km) for frequencies from 650 to 3350/cm-1.

Farmer, Crofton B.↗
DOE OSTI2020

Probing the Electronic Structure of a Thorium Nitride Complex by Solid-State 15N NMR Spectroscopy

The solid-state 15N NMR powder spectra of the thorium nitride complex, [K(18-crown-6)(THF)2][(R2N)3Th(m-15N)(Th(NR2)3] ([K][1-15N], R = SiMe3), and the thorium amide complex, [Th(NR2)3(15NH2)] (2-15N) were recorded. The spectrum for [K][1-15N] represents the first reported solid-state 15N NMR data for an actinide nitride complex. The experimentally measured tensor spans are 847 ppm for [K][1-15N] and 237 ppm for 2-15N. Both shielding tensors exhibit a near-zero asymmetry parameter, which for [K][1-15N] is consistent with a local rotational symmetry of its 15N-labelled nitride ligand. For 2-15N, the lack of asymmetry can be rationalized by a quasi-free Th-NH2 bond rotation in the solid-state. DFT calculations overestimate the tensor span somewhat for [K][1-15N], but provide isotropic shifts in good agreement with both the solid-state and solution values for both complexes. Natural localized molecular orbital (NLMO) analyses of the nuclear shielding reveal that the larger tensor span in [K][1-15N] vs. 2-15N is primarily a consequence of more pronounced covalency of the N-Th bonds, and large spin-orbit coupling due to significant Th 5f orbital contribution to those bonds, impacting the principal components of the shielding tensor perpendicular to the Th-N-Th axis. Overall, our analysis confirms the involvement of the 5f orbitals in Th-N multiple bonds, and further demonstrates the value of solid-state NMR spectroscopy for interrogating actinide-ligand bonding.

actinides, covalent bonding, Nuclear Magnetic Reso↗
DOE OSTI2021

Machine learning in materials science: From explainable predictions to autonomous design

The advent of big data and algorithmic developments in the field of machine learning (and artificial intelligence, in general) have greatly impacted the entire spectrum of physical sciences, including materials science. Materials data, measured or computed, combined with various techniques of machine learning have been employed to address a myriad of challenging problems, such as, development of efficient and predictive surrogate models for a range of materials properties, screening and down-selection of novel candidate materials for targeted applications, new methodologies to improve and further expedite molecular and atomistic simulations, with likely many more important developments to come in the foreseeable future. While the applications thus far have provided a glimpse of the true potential data-enabled routes have to offer, it has also become clear that further progress in this direction hinges on our ability to understand, explain and rationalize findings of a machine learning model in light of the domain-knowledge. This focused review provides an overview of the main areas where machine learning has been widely and successfully used in materials science. Subsequently, a brief discussion of several techniques that have been helpful in extracting physically-meaningful insights, causal relationships and design-centric knowledge from materials data is provided. Finally, we identify some of the imminent opportunities and challenges that materials community faces in this exciting and rapidly growing field.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Luminescence properties of europium doped and sodium co-doped LiCaAlF 6

This paper serves as a literature review of scintillating thermal neutron detectors, along with a study of sodium and europium doped LiCaAlF 6 (LiCAF) polycrystalline material. A set of polycrystalline LiCAF material was synthesized with 2 molar percent of europium (Eu 2+ ) and co-doped with 0, 1, and 2 molar percent of sodium (Na + ), with a stoichiometric synthesis approach in a glassy-carbon crucible. The quantum yield and photoluminescence spectrum at room temperature was analyzed. For the first time, we have demonstrated that Na-co-doping directly alters the quantum yield. The quantum yield for LiCAF:Eu 2+ , with 0, 1, and 2 molar percent of sodium (Na + ) was 0.578, 0.635, and 0.580, respectively. The photoluminescence (PL) spectrum was also analyzed for all samples. The photo-luminescence excitation (PLE) spectrum showed a maximum at 300 nm, while the emission spectrum showed a maximum at 370 nm, corresponding to the Eu 2+ 5d-4f transitions.

36 MATERIALS SCIENCE↗
NASA NTRS1978

Detection of the C4H radical toward IRC plus 10216

Four emission doublets in the millimeter-wave spectrum of IRC plus 10216 are identified as successive rotational transitions of the linear butadiynyl radical (C4H). The identifications are made on the basis of the agreement to within about 1 part in 1000 between the observed rotation constant of C4H and the value obtained from a Hartree-Fock calculation. A rough estimate of the amounts of C4H and C3N in the molecular envelope of IRC plus 10216 is given. The results indicate that C4H seems to be the more abundant species by about a factor of 4.

Guelin, M.↗
NASA NTRS1990

Optical and infrared spectrophotometry of the symbiotic system V1016 Cygni

Spectrophotometry from 0.46 to 1.3 micron of the peculiar emission-line object V1016 Cyg is presented. The optical region displays a weak continuum underlying the rich emission-line spectrum detailed in past studies. The infrared spectrum consists of prominent emission lines of H I, He I, He II, forbidden Ni, O I, and forbidden S III overlying a strong stellar continuum. The latter displays bands at 0.94 micron and 1.13 micron characteristic of a late-type, oxygen-rich giant as well as an absorption at 1.05 micron which is due to VO. The presence of these molecular features indicates a spectral class of M6 or later for the cool secondary. The reddening of the secondary does not appear to be much different from that of the emission lines. Among the infrared emission features is the rarely seen permitted transition of neutral oxygen at 1.1287 micron. Its presence at a strength comparable to O I 8446 A, together with the absence of O I 13164 A, confirms the result of Strafella that the strong O I lines arise primarily from fluorescent excitation by Ly-beta.

Rudy, Richard J.↗
NASA NTRS2007

Development of a Rayleigh Scattering Diagnostic for Time-Resolved Gas Flow Velocity, Temperature, and Density Measurements in Aerodynamic Test Facilities

A molecular Rayleigh scattering technique is developed to measure time-resolved gas velocity, temperature, and density in unseeded turbulent flows at sampling rates up to 32 kHz. A high power continuous-wave laser beam is focused at a point in an air flow field and Rayleigh scattered light is collected and fiber-optically transmitted to the spectral analysis and detection equipment. The spectrum of the light, which contains information about the temperature and velocity of the flow, is analyzed using a Fabry-Perot interferometer. Photomultiplier tubes operated in the photon counting mode allow high frequency sampling of the circular interference pattern to provide time-resolved flow property measurements. An acoustically driven nozzle flow is studied to validate velocity fluctuation measurements, and an asymmetric oscillating counterflow with unequal enthalpies is studied to validate the measurement of temperature fluctuations. Velocity fluctuations are compared with constant temperature anemometry measurements and temperature fluctuations are compared with constant current anemometry measurements at the same locations. Time-series and power spectra of the temperature and velocity measurements are presented. A numerical simulation of the light scattering and detection process was developed and compared with experimental data for future use as an experiment design tool.

Mielke, Amy F.↗