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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 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
NASA NTRS1998

A Very High Resolution Mid Infrared Spectrograph for SOFIA

The purpose of this project was to study the design of a high resolution mid-infrared spectrograph for the SOFIA airborne observatory. The primary motivation for the construction and use of such an instrument is the study of vibrational transitions of molecules in molecular clouds, circumstellar inflows and outflows, and planetary atmospheres, which are blocked from ground-based observations by absorption by the Earth's atmosphere. The instrument design studied is a cross-dispersed grating spectrograph with several modes of operation giving spectral resolving powers of approximately 4000, 20,000, and 100,000. In the two lower resolution modes a single grating is used in a long-slit spectrograph. At high resolution that grating serves as the cross-disperser for a 1-m long echelon, a very coarsely and steeply ruled grating, diamond-machined in aluminum. Several design study tasks were carried out: 1. An optical and mechanical design was developed. It differed from the preliminary design by using a reflecting focal reducer in the fore-optics and by rearranging the echelon and cross-dispersing chambers to improve the efficiency of the long-slit modes. 2. A finite-element analysis of the dewar and echelon support structures was done. It led us to change the echelon support to improve its rigidity. 3. Further information was obtained which convinced us that Hyperfine Inc. was capable of diamond-machining the echelon. 4. Several possible vendors of readout electronics and software were identified. It was decided that it is more cost-effective to purchase these items rather than developing them ourselves. 5. Observing and calibration procedures were studied. we did not identify significant changes needed from procedures used previously. 6. Possible expansions of instrument capabilities, including wavelength coverage, were studied. It appears unlikely that the echelon will perform well at wavelengths shortward of 5 microns, but the spectral coverage could be extended longward of 28 microns with the use of an Si:Sb detector. No patentable inventions were made during this study. Based on this design study, a proposal was submitted to construct the instrument. It was chosen as one of the first-light instruments for SOFIA.

Lacy, John H.↗
NASA NTRS1991

The Fundamental Quadrupole Band of (14)N2: Line Positions from High-Resolution Stratospheric Solar Absorption Spectra

The purpose of this note is to report accurate measurements of the positions of O- and S-branch lines of the (1-0) vibration-rotation quadrupole band of molecular nitrogen ((14)N2) and improved Dunham coefficients derived from a simultaneous least-squares analysis of these measurements and selected infrared and far infrared data taken from the literature. The new measurements have been derived from stratospheric solar occultation spectra recorded with Fourier transform spectrometer (FTS) instruments operated at unapodized spectral resolutions of 0.002 and 0.01 /cm. The motivation for the present investigation is the need for improved N2 line parameters for use in IR atmospheric remote sensing investigations. The S branch of the N2 (1-0) quadrupole band is ideal for calibrating the line-of-sight airmasses of atmospheric spectra since the strongest lines are well placed in an atmospheric window, their absorption is relatively insensitive to temperature and is moderately strong (typical line center depths of 10 to 50% in high-resolution ground-based solar spectra and in lower stratospheric solar occultation spectra), and the volume mixing ratio of nitrogen is constant in the atmosphere and well known. However, a recent investigation has'shown the need to improve the accuracies of the N2 fine positions, intensities, air-broadened half-widths, and their temperature dependences to fully exploit this calibration capability (1). The present investigation addresses the problem of improving the accuracy of the N2 line positions.

Rinsland, C. P.↗
NASA NTRS2019

Imaging the Key Stages of Planet Formation

New images of young stars are revolutionizing our understanding of planet formation. ALMA detects large grains in planet‐forming disks with few AU scale resolution and scattered light imaging with extreme adaptive optics systems reveal small grains suspended on the disks’ flared surfaces. Tantalizing evidence for young exoplanets is emerging from line observations of CO and H‐alpha. In this white paper, we explore how even higher angular resolution can extend our understanding of the key stages of planet formation, to resolve accreting circumplanetary disks themselves, and to watch planets forming in situ for the nearest star‐forming regions. We focus on infrared observations which are sensitive to thermal emission in the terrestrial planet formation zone and allow access to molecular tracers in warm ro‐vibrational states. Successful planet formation theories will not only be able to explain the diverse features seen in disks, but will also be consistent with the rich exoplanet demographics from RV and transit surveys. While we are far from exhausting ground‐based techniques, the ultimate combination of high angular resolution and high infrared sensitivity can only be achieved through mid‐infrared space interferometry.

John Monnier↗
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

Phonon-mediated lipid raft formation in biological membranes

Short-wavelength collective molecular motions, also known as phonons, have recently attracted much interest in revealing dynamic properties of biological membranes through the use of neutron and x-ray scattering, infrared and Raman spectroscopies, and molecular dynamics simulations. Experimentally detecting unique vibrational patterns such as, shear phonon excitations, viscoelastic crossovers, transverse acoustic phonon gaps, and continuous and truncated optical phonon modes in cellular membranes, to name a few, has proven non-trivial. Here, we review recent advances in liquid thermodynamics that have resulted in the development of the phonon theory of 1 liquids. The theory has important predictions regarding the shear vibrational spectra of fluids, namely the emergence of viscoelastic crossovers and transverse acoustic phonon gaps. Furthermore, we show that these vibrational patterns are common in soft (non-crystalline) materials, including, but not limited to liquids, colloids, liquid crystals (mesogens), block copolymers, and biological membranes. The existence of viscoelastic crossovers and acoustic phonon gaps define the self-diffusion properties of cellular membranes and provide a molecular picture of the transient nature of lipid rafts.1 Importantly, the timescales (picoseconds) for the formation and dissolution of transient lipid rafts match the lifetime of the formation and breakdown of interfacial water hydrogen bonds. Apart from acoustic propagating phonon modes, biological membranes can also support more energetic non-propagating optical phonon excitations, also known as standing waves or breathing modes. Importantly, optical phonons can be truncated due to the existence of finite size nanodomains made up of strongly correlated lipid-cholesterol molecular pairs. These strongly coupled molecular pairs can serve as nucleation centers for the formation of stable rafts at larger length scales, due to correlations of spontaneous fluctuations (Onsager’s regression hypothesis). Finally and importantly, molecular level viscoelastic crossovers, acoustic phonon gaps, and continuous and truncated optical phonon modes may offer insights as to how lipid-lipid and lipid-protein interactions enable biological function.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1988

Ratios of molecular hydrogen line intensities in shocked gas - Evidence for cooling zones

Column densities of molecular hydrogen have been calculated from 19 infrared vibration-rotation and pure rotational line intensities measured at peak 1 of the Orion molecular outflow. The run of column density with energy level is similar to a simple coolng zone model of the line-emitting region, but is not well fitted by predictions of C-shock models current in the literature.

Brand, P. W. J. L.↗
NASA NTRS1991

Study of cluster formation and its effects on Rayleigh and Raman scattering measurements in a Mach 6 wind tunnel

Using a frequency-doubled Nd-YAG pulsed laser and a single-intensified CCD camera, Rayleigh scattering measurements have been performed to study the cluster formation in a Mach 6 wind tunnel at NASA Langley Research Center. These studies were conducted both in the free stream and in a model flow field for various flow conditions to gain an understanding of the dependence of the Rayleigh scattering (by clusters) on the local pressures and temperatures in the facility. Using the same laser system, simultaneous measurements of the local temperature have also been performed using the rotational Raman scattering of molecular nitrogen and determined the densities of molecular oxygen and nitrogen by using the vibrational Raman scattering from these species. Quantitative results are presented in detail with emphasis on the applicability of the Rayleigh scattering for obtaining quantitative measurements of molecular densities both in the free stream and in the model flow field.

Shirinzadeh, B.↗
DOE OSTI2024

Adsorption, Orientation, and Speciation of Amino Acids at Air–Aqueous Interfaces for the Direct Air Capture of CO 2

Amino acids make up a promising family of molecules capable of direct air capture (DAC) of CO 2 from the atmosphere. Under alkaline conditions, CO 2 reacts with the anionic form of an amino acid to produce carbamates and deactivated zwitterionic amino acids. The presence of the various species of amino acids and reactive intermediates can have a significant effect on DAC chemistry, the role of which is poorly understood. In this study, all-atom molecular dynamics (MD) based computational simulations and vibrational sum frequency generation (vSFG) spectroscopy studies were conducted to understand the role of competitive interactions at the air–aqueous interface in the context of DAC. We find that the presence of potassium bicarbonate ions, in combination with the anionic and zwitterionic forms of amino acids, induces concentration and charge gradients at the interface, generating a layered molecular arrangement that changes under pre- and post-DAC conditions. In parallel, an enhancement in the surface activity of both anionic and zwitterionic forms of amino acids is observed, which is attributed to enhanced interfacial stability and favorable intermolecular interactions between the adsorbed amino acids in their anionic and zwitterionic forms. The collective influence of these competitive interactions, along with the resulting interfacial heterogeneity, may in turn affect subsequent capture reactions and associated rates. Finally, these effects underscore the need to consider dynamic changes in interfacial chemical makeup to enhance DAC efficiency and to develop successful negative emission and storage technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Densities and vibrational distribution of H(3+) in the Jovian auroral ionosphere

The assumption that H(3+) is in LTE in the region of the Jovian ionosphere from which the emissions originate is tested by calculating the vibrational distribution of H(3+) over the altitude range of 350 to 1500 km above the methane cloud tops. A model of the Jovian auroral ionosphere is constructed in which the neutral temperatures are enhanced over those of the midlatitude ionosphere, as suggested by observations and models of the auroral region. The energy and energy flux were found to be less than those involved in the production of the UV aurora. A computation of the densities and vibrational distribution shows that the distribution of the six lowest states of H(3+) can be determined fairly well in spite of uncertainties in the atomic and molecular data. The computed altitude profiles and vibrational distributions of H(3+) and H2 are consistent with the observations of IR emission in the 2- and 4-micron regions.

Kim, Y. H.↗
NASA NTRS1991

Study of Cluster Formation and its Effects on Rayleigh and Raman Scattering Measurements in a Mach 6 Wind Tunnel

Using a frequency-doubled Nd-YAG pulsed laser and a single-intensified CCD camera, Rayleigh scattering measurements have been performed to study the cluster formation in a Mach 6 wind tunnel at NASA Langley Research Center. These studies were conducted both in the free stream and in a model flow field for various flow conditions to gain an understanding of the dependence of the Rayleigh scattering (by clusters) on the local pressures and temperatures in the facility. Using the same laser system, we have also performed simultaneous measurements of the local temperature using the rotational Raman scattering of molecular nitrogen and determined the densities of molecular oxygen and nitrogen by using the vibrational Raman scattering from these species. Quantitative results will be presented in detail with emphasis on the applicability of the Rayleigh scattering for obtaining quantitative measurements of molecular densities both in the free stream and in the model flow field.

Shirinzadeh, B.↗
NASA NTRS1971

Quenching of vibrationally excited hydroxyl /v = 9/ with oxygen.

In the experiment discussed molecular oxygen was allowed to mix with atomic hydrogen and ozone at the entrance to a 3-m flow tube. A rate equation for the decay of the vibrationally excited hydroxyl is derived, taking into consideration the reaction with ozone, radiative decay, wall quenching, and interaction with molecular oxygen. It is pointed out that molecular oxygen might be important as a quencher for the hydroxyl airglow in the upper atmosphere in spite of negative results obtained in fast-flow experiments conducted in the laboratory.-

Worley, S. D.↗
DOE OSTI2022

Competitive Adsorption of NH 3 and H 2 O in Metal–Organic Framework Materials: MOF-74

Elucidating the interaction between coadsorbed H 2 O and NH 3 in metal–organic frameworks (MOFs) is of paramount importance to uncover mechanistic details of their competitive coadsorption behavior as well as to guide the design of new materials for enhanced NH 3 adsorption in humid environments. Nevertheless, molecular competition between NH 3 and H 2 O within the confined nanopores of MOFs was rarely explored and is poorly understood due to challenges in characterization. Here, we combine in situ infrared spectroscopy with ab initio calculations to unveil the competition of NH 3 and H 2 O for occupying active adsorption sites in the representative MOF-74 material by analyzing the kinetics and energetics of the molecular exchange process. We find that at a high NH 3 /H 2 O ratio, the incoming NH 3 is capable of displacing metal-bound H 2 O and moving it to secondary adsorption sites due to the stronger binding of NH 3 compared with H 2 O. Interestingly, the reverse process of H 2 O displacing metal-bound NH 3 is also possible upon increasing water concentration. Our calculations show that H 2 O exchanging the preabsorbed NH 3 at the metal site is driven not only by a reduced kinetic barrier but also by a favorable energetical state resulting from the formation of water clusters at metal sites and intermolecular H-bonding between the metal-coordinated H 2 O and displaced NH 3 . Our finding emphasizes that the description of molecular occupation in MOFs at equilibrium cannot simply be established by comparing molecules’ binding energies at their strongest binding sites derived by single-component measurements; rather, intermolecular interactions can greatly affect molecular distribution at equilibrium. Furthermore, we show that vibrational modes of adsorbed NH 3 are markedly perturbed upon contact with water molecules, accompanied by a large frequency shift (>30 cm –1 ) and considerable intensity decrease, which arises from the freezing of NH 3 vibrations by coadsorbed H 2 O. As a result, the mechanistic insight obtained through our study sheds light on molecular coadsorption processes in MOFs and helps to assess NH 3 removal efficiency of MOFs containing open-metal sites under realistic conditions, particularly in the presence of humidity.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Imaging a light-induced molecular elimination reaction with an X-ray free-electron laser

Tracking the motion of individual atoms during chemical reactions represents a severe experimental challenge, especially if several competing reaction pathways exist or if the reaction is governed by the correlated motion of more than two molecular constituents. Here we demonstrate how ultrashort X-ray pulses combined with coincident ion imaging can be used to trace molecular iodine elimination from laser-irradiated diiodomethane (CH 2 I 2 ), a reaction channel of fundamental importance but small relative yield that involves the breaking of two molecular bonds and the formation of a new one. We map bending vibrations of the bound molecule, disentangle different dissociation pathways, image the correlated motion of the iodine atoms and the methylene group leading to molecular iodine ejection, and trace the vibrational motion of the formed product. Our results provide a quantitative mechanistic picture behind previously suggested reaction mechanisms and prove that a variety of geometries are involved in the molecular bond formation.

Atomic and molecular interactions with photons↗
DOE OSTI2023

DFT-Based Calculation of Molecular Hyperpolarizability and SFG Intensity of Symmetric and Asymmetric Stretch Modes of Alkyl Groups

Vibrational sum frequency generation (SFG) spectroscopy has been extensively used for obtaining structural information of molecular functional groups at two-dimensional (2D) interfaces buried in the gas or liquid medium. Although the SFG experiment can be done elegantly, interpreting the measured intensity in terms of molecular orientation with respect to the lab coordinate is quite complicated. One of the main reasons is the difficulty of determining the hyperpolarizability tensors of even simple molecules that govern their SFG responses. The single-bond polarizability derivative (SBPD) model has been proposed to estimate the relative magnitude of SFG-active hyperpolarizability by assuming that the perturbation associated to each vibration is negligible. In this study, density functional theory (DFT) was used to calculate the polarizability and dipole derivative tensors of the CH 3 stretch mode of CH 3 I, CH 3 CH 2 I, CH 3 OH, CH 3 CH 2 OH. Then, the hyperpolarizability tensors of symmetric and asymmetric vibration modes were calculated considering the Boltzmann distribution of representative conformers, which allowed theoretical calculation of their SFG intensities at all polarization combinations as a function of the tilt angle of the CH 3 group with respect to the surface normal direction. Then the ratios of the calculated SFG intensities for the CH 3 peaks used in experimental studies for the CH 3 tilt angle determination were compared. This comparison clearly showed the effect of vibrational coupling among neighboring functional groups. As a result, this study presents new parameters that can be used in determining the average tilt angle of the CH 3 group at the 2D interface with SFG measurements as well as limitations of the method.

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

Trapping Ca + inside a molecular cavity: computational study of the potential energy surfaces for Ca + -[ n ]cycloparaphenylene, n = 5–12

Ion trap quantum computing utilizes electronic states of atomic ions such as Ca + to encode information on to a qubit. To explore the fundamental properties of Ca + inside molecular cavities, we describe here a computational study of Ca + bound inside neutral [n]-cycloparaphenylenes (n = 5–12), often referred to as “nanohoops”. This ab initio study characterizes optimized structures, harmonic vibrational frequencies, potential energy surfaces, and ion molecular orbital distortion as functions of increasing nanohoop size. Here the results of this work provide a first step in guiding experimental studies of the spectroscopy of these ion-molecular cavity complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2006

Isotope Effects in Collisional VT Relaxation of Molecular Hydrogen

A simple exponential-potential model of molecular collisions leads to a two-parameter analytic expression for rates of collisionally induced vibrational-translation (VT) energy exchange that has been shown to be accurate over variations of orders of magnitude as a function of temperature in a variety of systems. This includes excellent agreement with reported experimental and theoretical results for the fundamental self-relaxation rate of molecular hydrogen H2(v = 1) + H2 yields H2(v = 0) + H2. The analytic rate successfully follows the five-orders-of-magnitude change in experimental values for the temperature range 50-2000 K. This approach is now applied to isotope effects in the vibrational relaxation rates of excited HD and D2 in collision with H2: HD(v = 1)+H2 yields HD(v = 0)+H2 and D2(v = 1)+H2 yields D2(v = 0)+H2. The simplicity of the analytic expression for the thermal rate lends itself to convenient application in modeling the evolving vibrational populations of molecular hydrogen in shocked astrophysical environments.

Bieniek, R. J.↗
DOE OSTI2020

Capturing Deuteration Effects in a Molecular Mechanics Force Field: Deuterated THF and the THF–Water Miscibility Gap

Deuteration is a common chemical modification used in conjunction with experiments such as neutron scattering, NMR, and Fourier-transform infrared for the study of molecular systems. Under the Born–Oppenheimer (BO) approximation, while the underlying potential energy surface remains unchanged by isotopic substitutions, isotopic substitution still alters intramolecular vibrations, which in turn may alter intermolecular interactions. Molecular mechanics (MM) force fields used in classical molecular dynamics simulations are assumed to represent local approximations of the BO potential energy surfaces, and hence, MD simulations using simple isotopic mass substitutions should capture BO-compatible isotope effects. However, standard MM force-field parameterizations do not directly fit to the local harmonic quantum mechanical (QM) Hessian that describes the BO surface, but rather to QM normal-modes and/or mass-dependent internal-coordinate derived distortion energies. In this study, using tetrahydrofuran (THF)–water mixtures as our model system, we show that not only does a simple mass-substitution approach fail to capture an experimentally characterized deuteration effect (the loss of the closed-loop miscibility gap associated with the complete deuteration of THF) but also it is necessary to generate new MM force-field parameters that correctly describe isotopic dependent vibrations to capture the experimental deuteration effect. We show that the origin of this failure is a result of using mass-dependent features to fit the THF MM force field, which unintentionally biases the bonded terms of the force field to represent only the isotopologue used during the original force-field parameterization. In addition, we make use of our isotopologue-corrected force field for D 8 THF to examine the molecular origins of the isotope-dependent loss of the THF–water miscibility gap.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗