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At least 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
NASA NTRS1990

A further study of the molecular cloud associated with the supernova remnant G109.1-1.0

The region of the semicircular SNR G109.1-1.0 is studied on the basis of CO observations with a 45-m radio telescope and X-ray data from the archive of the Einstein Observatory. By observing the J = 1-0 transition of CO at 115 GHz, the distribution of the molecular cloud associated with the remnant is investigated in detail. The resolution of the CO mapping observations is 0.6-1.2 pc and the number of the CO spectra obtained is about 2000. The molecular ridge (CO arm), which was known to show an apparent anticorrelation with the curled x-ray jetlike feature of the remnant, is resolved into two CO filaments. The hardness of the X-ray spectrum toward the CO arm is consistent with the column densities of the two CO filaments. However, the overall appearance of the remnant will not be affected very much by the absorption, because the X-ray absorption is found to be a minor effect.

Tatematsu, Ken'ichi↗
NASA NTRS1992

FONO - A difficult case for theory and experiment

High levels of ab initio theory are used to investigate the equilibrium structures, vibrational spectra, and relative energetics of FNO2, cis-FONO, and trans-FONO isomers. FNO2 is determined to be 36.9 +/- 2.5 kcal/mol (0 K) more stable than cis-FONO, which is more stable than trans-FONO by 2.5 +/- 1.0 kcal/mol (0 K). The molecular structure of cis-FONO is shown to have typical F-O and central O-N single bond distances, indicating that cis-FONO has a structure analogous to HONO. The computed vibrational spectrum of cis-FONO is shown to be consistent with IR matrix isolation experiments, including isotopic shifts. The experimentally deduced structure of FONO is shown to be incorrect because one of the vibrational bands included in the normal coordinate analysis is either a combination band or an overtone.

Lee, Timothy J.↗
NASA NTRS1993

OPAD data analysis

Data obtained in the framework of an Optical Plume Anomaly Detection (OPAD) program intended to create a rocket engine health monitor based on spectrometric detections of anomalous atomic and molecular species in the exhaust plume are analyzed. The major results include techniques for handling data noise, methods for registration of spectra to wavelength, and a simple automatic process for estimating the metallic component of a spectrum.

Buntine, Wray L.↗
DOE OSTI2025

Polyyne production is regulated by the transcriptional regulators PgnC and GacA in Pseudomonas protegens Pf-5

ABSTRACT Polyynes produced by bacteria have promising applications in agriculture and medicine due to their potent antimicrobial activities. Polyyne biosynthetic genes have been identified inPseudomonasandBurkholderia. However, the molecular mechanisms underlying the regulation of polyyne biosynthesis remain largely unknown. In this study, we used a soil bacteriumPseudomonas protegensPf-5, which was recently reported to produce polyyne called protegenin, as a model to investigate the regulation of bacterial polyyne production. Our results show that Pf-5 controls polyyne production at both the pathway-specific level and a higher global level. Mutation ofpgnC, a transcriptional regulatory gene located in the polyyne biosynthetic gene cluster, abolished polyyne production. Gene expression analysis revealed that PgnC directly activates the promoter of polyyne biosynthetic genes. The production of polyyne also requires a global regulator GacA. Mutation ofgacAdecreased the translation of PgnC, which is consistent with the result thatpgnCleader mRNA bound directly to RsmE, an RNA-binding protein negatively regulated by GacA. These results suggest that GacA induces the expression of the PgnC regulator, which in turn activates polyyne biosynthesis. Additionally, the polyyne-producing strain of Pf-5, but not the polyyne-nonproducing strain, could inhibit a broad spectrum of bacteria including both Gram-negative and Gram-positive bacteria. IMPORTANCE Antimicrobial metabolites produced by bacteria are widely used in agriculture and medicine to control plant, animal, and human pathogens. Although bacteria-derived polyynes have been identified as potent antimicrobials for decades, the molecular mechanisms by which bacteria regulate polyyne biosynthesis remain understudied. In this study, we found that polyyne biosynthesis is directly activated by a pathway-specific regulator PgnC, which is induced by a global regulator GacA through the RNA-binding protein RsmE inPseudomonas protegens. To our knowledge, this work is the first comprehensive study of the regulatory mechanisms of bacterial polyyne biosynthesis at both pathway-specific level and global level. The discovered molecular mechanisms can help us optimize polyyne production for agricultural or medical applications.

Biotechnology & Applied Microbiology↗
DOE OSTI2021

The Low-Lying Electronic States of NO 2 : Potential Energy and Dipole Surfaces, Bound States, and Electronic Absorption Spectrum

Nitrogen dioxide, NO 2 , is a free radical composed of the two most abundant elements in Earth’s atmosphere, nitrogen and oxygen, and is relevant to atmospheric and combustion chemistry. The electronic structure of even its lowest-lying states is remarkably complex, with various conical intersections and Renner–Teller pairings, giving rise to complex and perturbed vibronic states. Here we report some analysis of the 18 molecular states of doublet spin-multiplicity formed by combining ground-state N( 4 S u ) and O( 3 P g ) atoms. In this work, three-dimensional potential energy surfaces were fit at the MRCI(Q)-F12/VTZ-F12 level, describing the lowest four ($\tilde X$, $\tilde A$, $\tilde B$, and $\tilde C$) electronic states. A properties-based diabatization procedure was applied to accommodate the intersections, producing energies in a quasidiabatic representation and yielding couplings that were also fit into surfaces. The low-lying vibrational levels on the ground $\tilde X$ state were computed and compared with experimental measurements. Compared to experiment, the lowest 125 calculated vibrational levels (up to 8500 cm –1 above the zero-point energy) have a root-mean-squared error of 16.5 cm –1 . In addition, dipole moments for each of the lowest four electronic states—and the transition dipoles between them—were also computed and fit. With the coupled energy and dipole surfaces, the electronic spectrum was calculated in absolute intensity and compared with experimental measurements. Detailed structure in the experimental spectrum was successfully reproduced, and the total integrated intensity matches experiment to an accuracy of ~1.5% with no empirical adjustments.

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

Vibronic Relaxation Pathways in Molecular Spin Qubit Na 9 [Ho(W 5 O 18 ) 2 ]·35H 2 O under Pressure

In order to explore how spectral sparsity and vibronic decoherence pathways can be controlled in a model qubit system with atomic clock transitions, we combined diamond anvil cell techniques with synchrotron-based far infrared spectroscopy and first-principles calculations to reveal the vibrational response of Na 9 [Ho(W 5 O 18 ) 2 ]·35H 2 O under compression. Because the hole in the phonon density of states acts to reduce the overlap between the phonons and f manifold excitations in this system, we postulated that pressure might move the HoO 4 rocking, bending, and asymmetric stretching modes that couple with the M J = ±5, ±2, and ±7 levels out of resonance, reducing their interactions and minimizing decoherence processes, while a potentially beneficial strategy for some molecular qubits, pressure slightly hardens the phonons in Na 9 [Ho(W 5 O 18 ) 2 ]·35H 2 O and systematically fills in the transparency window in the phonon response. The net result is that the vibrational spectrum becomes less sparse and the overlap with the various M J levels of the Ho 3+ ion actually increases. These findings suggest that negative pressure, achieved using chemical means or elongational strain, could further open the transparency window in this rare earth-containing spin qubit system, thus paving the way for the use of device surfaces and interface elongational/compressive strains to better manage decoherence pathways.

36 MATERIALS SCIENCE↗
DOE OSTI2020

The Terahertz Dynamics of an Aqueous Nanoparticle Suspension: An Inelastic X-ray Scattering Study

We used the high-resolution Inelastic X-ray Scattering beamline of the Advanced Photon Source at Argonne National Laboratory to measure the terahertz spectrum of pure water and a dilute aqueous suspension of 15 nm diameter spherical Au nanoparticles (Au-NPs). We observe that, despite their sparse volume concentration of about 0.5%, the immersed NPs strongly influence the collective molecular dynamics of the hosting liquid. We investigate this effect through a Bayesian inference analysis of the spectral lineshape, which elucidates how terahertz transport properties of water change upon Au-NP immersion. In particular, we observe a nearly complete disappearance of the longitudinal acoustic mode and a mildly decreased ability to support shear wave propagation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1975

The investigation of O and N2 densities from the OSO-7 extreme UV data

The results of solar radiation observations in the extreme ultra-violet spectrum from 200 A to 600 A made by the OSO-7 Satellite were studied. The results of the influence of attenuation by the atmosphere in the 250 to 500 km altitude range are presented. Using published molecular absorption cross-sections at 304 A and 256 A, the Jaccia atmospheric model is validated, and shows that a mean exospheric of 1050 K is appropriate for the sunset data.

Source record↗
NASA NTRS1979

Mass spectrometric investigation of the vaporization of sodium and potassium chromates: Preliminary results

Knudsen cell mass spectrometry was used to study the vaporization of sodium and potassium chromates. For both salts, the vaporization proceeds predominately by the reactions M2CrO4(c)=2M(g)+5/4O2(g)+1/2 Cr203(s) and M2CrO4(c)=M2CrO4(g) where M = Na or K. The distribution of the ions M(+), O2(+) and M2CrO4(+) in the measured mass spectrum was found to depend on the material used for the Knudsen cell, even for materials such as platinum and gold. In the case of sodium chromate, the decomposition reaction appears to be less important than the molecular vaporization reaction. A preliminary value of 72 kcal/mole at 1141 K was measured for the heat of the molecular vaporization reaction for sodium chromate. In the case of potassium chromate, it has not been possible to conclude which mode of vaporization dominates. For potassium chromate a value of 101 kcal/mole at 1173 K was obtained for the heat of the molecular vaporization reaction.

Stearns, C. A.↗
NASA NTRS2014

X-Ray Absorption near Edge Structure Spectroscopic Study of Hayabusa Category 3 Carbonaceous Particles

Analyses with a scanning transmission x-ray microscope (STXM) using x-ray absorption near edge structure (XANES) spectroscopy were applied for the molecular characterization of two kinds of carbonaceous particles of unknown origin, termed category 3, which were collected from the Hayabusa spacecraft sample catcher. Carbon-XANES spectra of the category 3 particles displayed typical spectral patterns of heterogeneous organic macromolecules; peaks corresponding to aromatic/olefinic carbon, heterocyclic nitrogen and/or nitrile, and carboxyl carbon were all detected. Nitrogen-XANES spectra of the particles showed the presence of N-functional groups such as imine, nitrile, aromatic nitrogen, amide, pyrrole, and amine. An oxygen-XANES spectrum of one of the particles showed a ketone group. Differences in carbon- and nitrogen-XANES spectra of the category 3 particles before and after transmission electron microscopic (TEM) observations were observed, which demonstrates that the carbonaceous materials are electron beam sensitive. Calcium-XANES spectroscopy and elemental contrast mapping identified a calcium carbonate grain from one of the category 3 particles. No fluorine-containing molecular species were detected in fluorine-XANES spectra of the particles. The organic macromolecular features of the category 3 particles were distinct from commercial and/or biological ‘fresh (non-degraded)’ polymers, but the category 3 molecular features could possibly reflect degradation of contaminant polymer materials or polymer materials used on the Hayabusa spacecraft. However, an extraterrestrial origin for these materials cannot currently be ruled out.

Asteroides↗
DOE OSTI2022

Modeling the Electronic Absorption Spectra of the Indocarbocyanine Cy3

Accurate modeling of optical spectra requires careful treatment of the molecular structures and vibronic, environmental, and thermal contributions. The accuracy of the computational methods used to simulate absorption spectra is limited by their ability to account for all the factors that affect the spectral shapes and energetics. The ensemble-based approaches are widely used to model the absorption spectra of molecules in the condensed-phase, and their performance is system dependent. The Franck–Condon approach is suitable for simulating high resolution spectra of rigid systems, and its accuracy is limited mainly by the harmonic approximation. In this work, the absorption spectrum of the widely used cyanine Cy3 is simulated using the ensemble approach via classical and quantum sampling, as well as, the Franck–Condon approach. The factors limiting the ensemble approaches, including the sampling and force field effects, are tested, while the vertical and adiabatic harmonic approximations of the Franck–Condon approach are also systematically examined. Our results show that all the vertical methods, including the ensemble approach, are not suitable to model the absorption spectrum of Cy3, and recommend the adiabatic methods as suitable approaches for the modeling of spectra with strong vibronic contributions. We find that the thermal effects, the low frequency modes, and the simultaneous vibrational excitations have prominent contributions to the Cy3 spectrum. The inclusion of the solvent stabilizes the energetics significantly, while its negligible effect on the spectral shapes aligns well with the experimental observations.

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

Terahertz Circular Dichroism Spectroscopy of Molecular Assemblies and Nanostructures

Chemical, physical, biological and materials engineering disciplines use a variety of chiroptical spectroscopies to probe geometrical and optical asymmetry in molecules and particles. Electronic (ECD) and vibrational (VCD) circular dichroism are the most common of these techniques and collectively enable the studies of electronic and vibronic transitions with energies between 0.1 and 5.0 eV. The vibrational states with characteristic energies in the range of 0.001–0.01 eV carry valuable information about concerted intermolecular motions in molecules and crystals involving multiple atoms. These vibronic transitions located in the terahertz (THz) part of the spectrum become increasingly more important for the chemistry, physics, and biology of complex molecules and materials However, the methodology and hardware of THz circular dichroism (TCD) are much less developed than the chiroptical spectroscopies for ultraviolet, visible, near- and mid infrared photons. In this report we provide theoretical foundations, practical implementations, comparative assessments, and exemplary applications of TCD spectroscopy. We show that the sign, intensity, and position of TCD peaks are highly sensitive to the three-dimensional structure and long-range organization of molecular crystals, which offer unique capabilities to study (bio) molecules, their crystals, and nanoscale assemblies and apply the novel data processing methodologies. TCD also offers a convenient toolbox to identify new physical phenomena, such as chiral phonons and their propagation in nanostructured matter. We also discuss the major challenges, emerging opportunities and promising research directions, including broad investigation of chiral phonons observed in chiral (nano) crystals and emerging machine learning methodologies for TCD in biological and nanoscale structures. Ubiquity of low-frequency vibrations with rotational components in biomolecular structures, combined with sharpness of peaks in TCD spectra, enables a variety of technological translations.

36 MATERIALS SCIENCE↗
NASA NTRS1983

The 12 micron band of ethane: A spectral catalog from 765 cm(-1) to 900 cm(-1)

The high resolution laboratory absorption spectrum of the 12 micro band of ethane gas is studied. The data were obtained using the McMath Solar Telescope 1 meter Fourier Transform interferometer at Kitt Peak National Observatory and tunable diode laser spectrometers at the University of Tennessee and NASA/Goddard Space Flight Center. Over 200 individual vibration rotation transitions were analyzed taking into account many higher order effects including torsional splitting. Line positions were reproduced to better than 0.001/cm. Both ground and upper state molecular constants were determined in the analysis. The experimental details, the analysis procedures and the results are addressed. A list of ethane transitions occurring near (14)CO2 laser lines needed for heterodyne searches for C2H6 in extraterrestrial sources is also included. A spectral catalog of the ethane nu sub g fundamental from 765/cm to 900/cm is provided. A high dispersion (1/cm 12 in.) plot of both the Kitt Peak interferometric data and a simulated spectrum with Doppler limited resolution, a table of over 8500 calculated transitions listed quantum number assignments, frequencies and intensities are provided.

Atakan, A. K.↗
NASA NTRS2008

Laser Infrared Desorption Spectroscopy to Detect Complex Organic Molecules on Icy Planetary Surfaces

Laser Desorption-Infrared Spectroscopy (LD-IR) uses an IR laser pulse to desorb surface materials while a spectrometer measures the emission spectrum of the desorbed materials (Figure 1). In this example, laser desorption operates by having the incident laser energy absorbed by near surface material (~10 microns in depth). This desorption produces a plume that exists in an excited state at elevated temperatures. A natural analog for this phenomenon can be observed when comets approach the sun and become active and individual molecular emission spectra can be observed in the IR [1,2,3,4,5]. When this occurs in comets, the same species that initially emit radiation down to the ground state are free to absorb it, reducing the amount of detectable emission features. The nature of our technique results in absorption not occurring, because the laser pulse could easily be moved away form the initial desorption plume, and still have better spatial resolution then reflectance spectroscopy. In reflectance spectroscopy, trace components have a relatively weak signal when compared to the entire active nature of the surface. With LDIR, the emission spectrum is used to identify and analyze surface materials.

Laser Desorption-Infrared Spectroscopy↗
DOE OSTI2024

Design, Control and Application of Next Generation Qubits

Design, Control and Application of Next Generation Qubits Arun Bansil, Northeastern University (Principal Investigator) Claudio Chamon, Boston University (Co-Investigator) Adrian Feiguin, Northeastern University (Co-Investigator) Liang Fu, MIT (Co-Investigator) Eduardo Mucciolo, Univ. of Central Florida (Co-Investigator) Qimin Yan, Temple University (Co-Investigator) The quest for developing technologies for manipulating and storing information quantum mechanically is currently led by approaches that include Josephson-junctions, ion-traps, and qubits generated by defect spins in solids. Topological qubits, however, are inherently more robust to decoherence by environmental effects, and should be able to sprint ahead once practical barriers have been overcome. At the present stage of the development of the field, it is important to explore a variety of architectures and materials beyond the conventional paradigms in order to seed breakthroughs toward building a scalable quantum computer. Our comprehensive theoretical research program involved four interconnected thrusts as follows. • A materials discovery effort in two-dimensional compounds in search of materials to support Majorana zero modes and defect structures suitable as qubits. • Exploration of architectures for topological quantum computation by investigating both superconducting Majorana qubits, and robust platforms for braiding with new “meta-materials” built of arrays of Majorana qubits. • Investigation of properties of hybrid metal-organic qubits based on transition-metal centers in graphene, and molecular crystals of polyaromatic complexes with embedded transition-metal atoms. • Development of tensor-network and semiclassical approaches to study decoherence in the presence of random and dispersive spin baths, and NV centers in diamond. The full spectrum of theoretical and numerical approaches was used to address the goals of this project including first-principles, density-matrix-renormalization group, tensor networks, and data-driven high-throughput approaches using materials database and machine-learning.

36 MATERIALS SCIENCE↗
NASA NTRS1979

High resolution atmospheric transmission calculations down to 28.7 km in the 200-243-nm spectral range

Decrease in stratospheric ozone absorption and increase in oxygen absorption with decreasing wavelength combine to produce a window of maximum atmospheric transmission near 210 nm. Since solar radiation in this spectral region dissociates molecular oxygen, the deep atmospheric penetration at this wavelength is of particular aeronomical interest. High resolution calculations of the transmittance down to 28.65 km were made for the 200-243-nm spectral range in this window region, in support of a stratospheric balloon flight from Fort Churchill in July 1974. The calculations were made by dividing the atmosphere into layers which were chosen so that each could be assumed homogeneous; optical depths were calculated separately for each of these layers and then summed to obtain the over-all transmittance of the atmosphere. Absorption by molecular oxygen (line and continuum) and by ozone was included, as well as extinction through Rayleigh scattering by air molecules. The calculated transmittances were combined with high altitude (above 100-km) rocket measurements of the sun-center spectrum and center-to-limb variations to give residual high resolution solar spectral flux for several altitudes and solar zenith angles.

Cann, M. W. P.↗
NASA NTRS1983

The adsorption and thermal decomposition of tricresylphosphate (TCP) on iron and gold

Because tricresyl-phosphate (TCP) is a common antiwear additive in lubricants, there is great interest in its interactions with metal substrates. The TCP was allowed to adsorb on polycrystalline iron and gold at room temperature. X-ray photoelectron spectroscopy (XPS) was used to analyze the adsorbed species. The substrate was then heated in steps to 330 C, and the changes in the adsorbate were analyzed after each step. On both substrates saturation adsorption occurred at about one monolayer, but the sticking coefficient was less on gold than on iron. Comparison of the XPS spectra of TCP on each substrate with the spectrum from condensed TCP indicated nondissociative adsorption on gold, possibly by dipole-induced dipole interaction. On iron, there was apparently additional interaction between the substrate and the tolyl groups on the TCP molecule. TCP began to desorb molecularly from gold as soon as the gold was heated above room temperature. The desorption was complete by 200 C. However, when the iron substrate was heated, TCP did not desorb but decomposed between 150 and 250 C.

Wheeler, D. R.↗
NASA NTRS1991

Energy deposition by X-ray photoelectrons into interstellar molecular clouds

The deposition of energy by 100-10,000 eV electrons into molecular hydrogen and helium gas of cosmic abundances and fractional ionization ranging from 10 to the -12th to 0.1 is considered. In order to account for energy deposition by both discrete and continuous degradation processes, the loss spectrum, a form of the Spencer-Fano degradation spectrum particularly suited to describing electron energy deposition in a partially ionized gas is considered. The calculated excitation and ionization yields drop as the fractional ionization increases. The dependences of these yields on fractional ionization are fitted to a form suitable for swift numerical computation.

Voit, G. M.↗