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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS1980

Infrared molecular absorption features

Spectra of infrared sources associated with molecular clouds have shown absorption features at wavelengths of 6.0 and 6.8 microns. It is suggested that the 6.0 micron feature can be identified with the stretching vibration of C = 0 and the 6.8 micron feature with the bending vibrations of CH2 and CH3. The amount of carbon in the form of hydrocarbon molecules may be comparable to the amount in CO. This abundance of hydrocarbons is probably too large to be consistent with radio observations if the molecules are gaseous, but large abundances of hydrocarbons on the surfaces of grains may explain the infrared features, and yet be unobservable in the radio.

Willner, S. P.↗
NASA NTRS1990

Laboratory simulation of interstellar grain chemistry and the production of complex organic molecules

During the past 15 years considerable progress in observational techniques has been achieved in the middle infrared (5000 to 500 cm(-1), 2 to 20 microns m), the spectral region most diagnostic of molecular vibrations. Spectra of many different astronomical infrared sources, some deeply embedded in dark molecular clouds, are now available. These spectra provide a powerful probe, not only for the identification of interstellar molecules in both the gas solid phases, but also of the physical and chemical conditions which prevail in these two very different domains. By comparing these astronomical spectra with the spectra of laboratory ices one can determine the composition and abundance of the icy materials frozen on the cold (10K) dust grains present in the interior of molecular clouds. These grains and their ice mantles may well be the building blocks from which comets are made. As an illustration of the processes which can take place as an ice is irradiated and subsequently warmed, researchers present the infrared spectra of the mixture H2O:CH3OH:CO:NH3:C6H14 (100:50:10:10:10). Apart from the last species, the ratio of these compounds is representative of the simplest ices found in interstellar clouds. The last component was incorporated into this particular experiment as a tracer of the behavior of a non-aromatic hydrocarbon. The change in the composition that results from ultraviolet photolysis of this ice mixture using a UV lamp to simulate the interstellar radiation field is shown. Photolysis produces CO, CO2, CH4, HCO, H2CO, as well as a family of moderately volatile hydrocarbons. Less volatile carbonaceous materials are also produced. The evolution of the infrared spectrum of the ice as the sample is warmed up to room temperature is illustrated. Researchers believe that the changes are similar to those which occur as ice is ejected from a comet and warmed up by solar radiation. The warm-up sequence shows that the nitrile or iso-nitrile bearing compound produced during photolysis evaporates between 200 and 250K, suggesting that it is carried by a small molecular species. These molecules could be similar to the source material in Comet Halley that is ejected in grains into the coma, freed by sublimation, and photolyzed by solar radiation to produce the observed jets.

Allamandola, L. J.↗
DOE OSTI2023

Electronic spectroscopy and ionization potentials for YbOH and YbOCH 3

The polyatomic molecules YbOH and YbOCH 3 have been recognized as being of potential value for spectroscopic experiments that explore charge-parity and time reversal symmetry violation effects. These measurements require very high precision, which, in turn, will necessitate that the molecules be manipulated at ultra-cold temperatures. Both YbOH and YbOCH 3 have electronic transitions that appear suitable for laser cooling ($\tilde{A}$ 2 Π 1/2 -$\tilde{X}$ 2 Σ + and $\tilde{A}$2E 1/2 -$\tilde{X}$ 2 A 1 , respectively) but the currently available spectroscopic data is not sufficient to determine the extent to which population leaks may compromise the optical cooling processes. A further complication is that the quantum states of interest for these measurements will need to be selectively populated. The $\tilde{A}$-$\tilde{X}$ band systems of both YbOH and YbOCH 3 show evidence of vibronic perturbations, such that there are unassigned vibronic features at energies that are just above the origin bands. Here, in the present study we have recorded spectra for the $\tilde{A}$ 2 Π 1/2 -$\tilde{X}$ 2 Σ + transition of jet-cooled YbOD to facilitate the vibronic assignments. In addition, spectra for the $\tilde{B}$ 2 Σ + - $\tilde{X}$ 2 Σ + transition of YbOH were recorded, establishing the origin band at 20473.8 cm -1 . Previously, the reaction of Yb with CH 3 OH has been used to generate gas-phase YbOCH 3 . As this reaction also yields YbOH, there have been complications in spectroscopic studies of YbOCH 3 due to overlap of the $\tilde{A} -\tilde{X}$ band systems. To identify specific regions of overlap, resonantly enhanced two-photon ionization spectra were recorded using mass-resolved detection of the YbOH + and YbOCH 3 + ions. These data confirmed the overlap of vibronic bands near 17640 and 17680 cm -1 . Two-photon ionization spectroscopy also provided accurate ionization energies of IE(YbOH)=45788(10) and IE(YbOCH 3 )=45283(10) cm -1 . The IE for YbOH is relevant to problems encountered in previous attempts to determine the bond dissociation energy of YbOH + .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1977

Computer programs for the interpretation of low resolution mass spectra: Program for calculation of molecular isotopic distribution and program for assignment of molecular formulas

Two FORTRAN computer programs for the interpretation of low resolution mass spectra were prepared and tested. One is for the calculation of the molecular isotopic distribution of any species from stored elemental distributions. The program requires only the input of the molecular formula and was designed for compatability with any computer system. The other program is for the determination of all possible combinations of atoms (and radicals) which may form an ion having a particular integer mass. It also uses a simplified input scheme and was designed for compatability with any system.

Miller, R. A.↗
NASA NTRS1979

On the possibility of analytical approximation of line forms during random disorders of the resonance frequencies in molecular vibration-rotation spectra for satellite sounding

The generalization spectral line contour concept and formulas for a two component mixture, as well as consequences of the general formula are discussed. The calculation procedure, initial information, calculation results and comparison of calculations with available experimental data, for radiation absorption in three CO2 bands are presented.

Fomin, V. V.↗
DOE OSTI2023

X-ray Thomson scattering spectra from density functional theory molecular dynamics simulations based on a modified Chihara formula

Here, we study ab initio approaches for calculating x-ray Thomson scattering spectra from density functional theory molecular dynamics simulations based on a modified Chihara formula that expresses the inelastic contribution in terms of the dielectric function. We study the electronic dynamic structure factor computed from the Mermin dielectric function using an ab initio electron-ion collision frequency in comparison to computations using a linear-response time-dependent density functional theory (LR-TDDFT) framework for hydrogen and beryllium and investigate the dispersion of free-free and bound-free contributions to the scattering signal. A separate treatment of these contributions, where only the free-free part follows the Mermin dispersion, shows good agreement with LR-TDDFT results for ambient-density beryllium, but breaks down for highly compressed matter where the bound states become pressure ionized. LR-TDDFT is used to reanalyze x-ray Thomson scattering experiments on beryllium demonstrating strong deviations from the plasma conditions inferred with traditional analytic models at small scattering angles.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Can machine learning predict fuel properties accurately?

High-potential molecules derived from biomass sources may suitably replace or supplement traditional nonrenewable hydrocarbon fuels to reduce pollution and fuel processing cost. Experimental property testing of these bioproducts is usually conducted years after initial bench-scale experiments, due to high experimental costs and/or high volume requirements. However, neglecting to conduct property testing early in the pathway development cycle can lead to investments spent on scaling-up production of bioproducts and biofuels that do not perform as expected. Instead, machine-learning techniques can be used to develop quantitative structure–property relationships for molecules using a relatively large training set of molecular descriptor data. For this study, we compiled measured properties, IR spectra, and molecular descriptors of bio-based molecules from databases and published studies for training models of bioproduct properties. We trained regression models with molecular descriptors and will compare results of different estimators. This study describes the first steps towards a performance prediction tool for bio-based alternative fuels. Keywords: Machine learning, biofuels, jet fuels, fuel properties

Mayer, Morgan A.↗
NASA NTRS1982

Application of ion-induced nucleation mass spectrometry in the analysis of trace gases evolved from a polyimide film during the thermal curing stages

Trace gases evolved from a polyimide film during its thermal curing stages have been studied using ion-induced nucleation mass spectrometry. The technique involved exposing the test gas sample to a low energy beta source and recording the masses of the ion-induced molecular clusters formed in the reaction chamber. On the basis of the experimentally observed molecular cluster spectra, it has been concluded that the dominant trace component had a molecular weight of 87 atomic mass units. This component has been identified as a molecule of dimethylacetamide (DMAC) which had been used as a solvent in the preparation of the test polyimide specimen. This identification has been further confirmed by comparing the spectra of the test gas sample and the DMAC calibration sample obtained with a conventional mass spectrometer. The advantages of the ion-induced nucleation mass spectrometer versus the conventional mass spectrometer are discussed.

Smith, A. C.↗
NASA NTRS2011

The Interstellar Bullet Engine IRAS 05506+2414

Throughout their life-cycles, high-mass stars inject large amounts of energy and momentum into theirenvironments through stellar winds. Results from a study of the Orion BN/KL region indicate that disruption of a massive young stellar system can lead to an explosive event producing a wide-angle outflow, different from the classical bipolar flows driven by young stellar object (YSO) accretion disks. The discovery of a massive YSO, IRAS 05506+2414, may prove to be the second instance of this uncommon outflow. Prior to this study, data was collected using the Arizona Radio Observatory's 10-meter and 12-meter telescopes. Spectra of 16 different molecular line transitions were organized, reduced, and prepared for further analysis. A variety of molecular transitions were observed, such as 12CO 2-1, HCO+ 3-2, CS 3-2, in order to probe physical conditions of the YSO. From line transitions like HCO+ 3-2, we will determine physical properties like density, temperature, and velocity of our source object. For each molecular transition, the spectra were averaged in subsets, which were then averaged to produce a final spectra with an optimal signal to noise ratio. Future radiative modeling will yield mass and energetics of IRAS05506+2414.

millimeter-wave↗
NASA NTRS1982

Measurement of the dispersive and refractive indices of germanium using diode lasers

Germanium Fabry-Perot etalons are commonly used in diode laser spectroscopy to establish relative frequency calibration scales for molecular absorption spectra. Typically the channel spectrum of the etalon is recorded simultaneously with the molecular spectrum as the laser injection current is tuned linearly, and the etalon free spectral range (fringe spacing) is used to measure the frequency separations among lines in the molecular spectrum. For this purpose, the etalon free spectral range must be known for the measurement wavelength, and this in turn relies on knowledge of the etalon length and the dispersive index at this wavelength. It is pointed out that the most satisfactory approach is to measure directly the free spectral range or dispersive index of the etalon at the wavelength of interest. A description is presented of measurements of this type, performed near 7.9 and 10.1 micrometers for a 7.7-cm long germanium etalon.

Jennings, D. E.↗
DOE OSTI2021

Li Isotope Signatures using Optical Spectroscopies

The primary goal of this work is to investigate the detection capabilities of laser ablation molecular isotopic spectrometry (LAMIS) and Raman spectroscopy for lithium isotopic determination as related to Li enrichment activities. LAMIS is an emerging spectroscopic technique that takes advantage of the fact that molecules exhibit much larger isotopic wavelength shifts in molecular emission spectra than their atomic counterparts. Raman spectroscopy has been shown to exhibit isotopic shifts if a given molecular vibration involves the isotope of interest. Both techniques are comprised of the same basic hardware: a spectrometer, a laser system (pulsed for LAMIS, pulsed or CW for Raman), and an intensified charge-coupled device (ICCD). Shifts in Raman spectra due to lithium isotopes in Li 2 C0 3 and LiOH*H 2 0 were observed. LAMIS measurements of the same compounds have not been successful yet, as no lithium containing molecular emissions have been identified to this point. However, an isotopic shift of the self-reversal of an atomic lithium emission was observed, which is another optical technique used to measure isotopes.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2022

Real-time equation-of-motion CC cumulant and CC Green’s function simulations of photoemission spectra of water and water dimer

Newly developed coupled-cluster (CC) methods enable simulations of ionization potentials and spectral functions of molecular systems in a wide range of energy scales ranging from core-binding to valence. This paper discusses the results obtained with the real-time equation-of-motion CC cumulant (RT-EOM-CC) approach and CC Green’s function (CCGF) approaches in applications to the water and water dimer molecules. Here, we compare the ionization potentials obtained with these methods for the valence region with the results obtained with the coupled-cluster with singles, doubles, and perturbative triples formulation as a difference of energies for N and N – 1 electron systems. All methods show good agreement with each other. They also agree well with the experiment with errors usually below 0.1 eV for the ionization potentials. We also analyze unique features of the spectral functions, associated with the position of satellite peaks, obtained with the RT-EOM-CC and CCGF methods employing single and double excitations, as a function of the monomer OH bond length and the proton transfer coordinate in the dimer. Finally, we analyze the impact of the basis set effects on the quality of calculated ionization potentials and find that the basis set effects are less pronounced for the augmented-type sets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Photoelectron spectra of early 3 d -transition metal dioxide molecular anions from GW calculations

Photoelectron spectra of early 3 d -transition metal dioxide anions, Sc O 2 - , Ti O 2 - , V O 2 - , Cr O 2 - , and Mn O 2 - , are calculated using semilocal and hybrid density functional theory (DFT) and many-body perturbation theory within the GW approximation using one-shot perturbative and eigenvalue self-consistent formalisms. Different levels of theory are compared with each other and with available photoelectron spectra. We show that one-shot GW with a PBE0 starting point ( G 0 W 0 @PBE0) consistently provides very good agreement for all experimentally measured binding energies (within 0.1 eV–0.2 eV or less). We attribute this to the success of PBE0 in mitigating self-interaction error and providing good quasiparticle wave functions, which renders a first-order perturbative GW correction effective. One-shot GW calculations with a Perdew–Burke–Ernzerhof (PBE) starting point do poorly in predicting electron removal energies by underbinding orbitals with typical errors near 1.5 eV. A higher exact exchange amount of 50% in the DFT starting point of one-shot GW does not provide very good agreement with experiment by overbinding orbitals with typical errors near 0.5 eV. While not as accurate as G 0 W 0 @PBE0, the G -only eigenvalue self-consistent GW scheme with W fixed to the PBE level provides a reasonably predictive level of theory (typical errors near 0.3 eV) to describe photoelectron spectra of these 3 d -transition metal dioxide anions. Adding eigenvalue self-consistency also in W , on the other hand, worsens the agreement with experiment overall. Overall, our findings on the performance of various GW methods are discussed in the context of our previous studies on other transition metal oxide molecular systems.

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

Scaling Ensembles of Data-Intensive Quantum Chemical Calculations for Millions of Molecules

Deep learning models are efficient computational tools that can accelerate the inverse design of molecules with desired functional properties by generating predictions at a fraction of the time required by traditional quantum chemical approaches. To ensure that a model maintains accuracy and transferability across broad regions of the chemical space explored during the inverse design, it must be trained on massively large volumes of simulation data. This requires running large-scale ensemble quantum chemical calculations on high-performance computing (HPC) systems for data collection. However, the efficient execution of such large ensemble calculations and the management of large volumes of output data require tools that can judiciously utilize computational resources and manage metadata overhead on the file system. Therefore, we present a high-performance, scalable, ensemble management framework for performing data-intensive quantum chemical electronic structure calculations for organic molecules. This framework provides abstractions to plug different ab initio, first principles, and first principles-based semi-empirical methods and executes them efficiently at large scale on HPC systems. It dynamically distributes tasks to resources and uses tiered storage for managing large collections of files. We employed this framework to process over ten million organic molecules and generate open-source datasets that provide UV-vis absorption spectra by running time-dependent density-functional tight-binding calculations. It is the largest database containing molecular optical spectra that were simulated with quantum chemical methods in a consistent manner.

Mehta, Kshitij↗
DOE OSTI2020

Momentum-resolved above-threshold ionization of deuterated water

We present momentum-resolved coincidence measurements of strong-field single and double ionization of deuterated water (D 2 O) using intense few-cycle laser pulses. We measure the vector momentum of electrons and ions resulting from the laser-molecule interaction. This enables us to measure the photoelectron spectrum for electrons in coincidence with fragment ions having different momenta, which can be related to different final states of the cation and dication. The photoelectron spectra for different fragment ion momenta show striking differences, which can be interpreted in terms of the removal of electrons from different molecular orbitals, including the highest occupied molecular orbital (HOMO), as well as more deeply bound ones (e.g., HOMO-2). Here, we discuss our measurements in light of calculations which model the strong-field light matter interaction.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1988

Interstellar grain chemistry and the composition of comets

During the past 15 years considerable progress in observational techniques has been achieved in the middle infrared, the spectral region most diagnostic of molecular vibrations. Spectra of many different astronomical infrared sources are now available. By comparing these astronomical spectra with the spectra of lab ices, one can determine the composition and abundance of the icy materials frozen on the cold dust grains present in the interior of molecular clouds. In the experiments described, the assumption is made that cometary ices are similar to interstellar ices. As an illustration of the processes which can take place as an ice is irradiated and subsequently warmed, the infrared spectra is presented of the mixture H2O:CH3OH:CO:NH3:C6H14 (100:50:10:10:10). Apart from the last species, the ratio of these compounds is representative of the simplest ices found in interstellar clouds.

Allamandola, Louis J.↗