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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
NASA NTRS2001

In Situ Measurements of Meteoric Ions

Metal ions found in the atmosphere above 60 km are the result of incoming meteoroid atmospheric ablation. Layers of metal ions are detected by sounding rocket in situ mass spectrometric sampling in the 80 to 130 km region, which coincides with the altitude region where meteors are observed. Enhancements of metal ion concentrations occur during meteor showers. Even outside of shower periods, the metal ion altitude profiles vary from measurement to measurement. Double layers are frequent at middle latitudes. More than 40 different meteoric atomic and molecular ions, including isotopes, have been detected. Atmospheric metal ions on average have an abundance that matches chrondritic material, the same composition as the early solar system. However there are frequently local departures from this composition due to differential ablation, species dependent chemistry and mass dependent ion transport. Metal ions react with atmospheric O2, O, O3, H2O and H2O2 to form oxygenated and hydrogenated ionic compounds. Metal atomic ions at high altitudes have long lifetimes. As a result, these ions, in the presence of Earth's magnetic field, are transported over long distances by upper atmospheric winds and ionospheric electric fields. Satellite measurements have detected metal ions as high as, approximately 1000 km and have revealed circulation of the ions on a global scale.

Grebowsky, Joseph M.↗
DOE OSTI2021

Long-range model of vibrational autoionization in core-nonpenetrating Rydberg states of NO

In high orbital angular momentum (ℓ ≥ 3) Rydberg states, the centrifugal barrier hinders the close approach of the Rydberg electron to the ion-core. As a result, these core-nonpenetrating Rydberg states can be well described by a simplified model in which the Rydberg electron is only weakly perturbed by the long-range electric properties (i.e., multipole moments and polarizabilities) of the ion-core. We have used a long-range model to describe the vibrational autoionization dynamics of high-ℓ Rydberg states of nitric oxide (NO). In particular, our model explains the extensive angular momentum exchange between the ion-core and the Rydberg electron that had been previously observed in vibrational autoionization of f (ℓ = 3) Rydberg states. These results shed light on a long-standing mechanistic question around these previous observations and support a direct, vibrational mechanism of autoionization over an indirect, predissociation-mediated mechanism. In addition, our model correctly predicts newly measured total decay rates of g (ℓ = 4) Rydberg states because for ℓ ≥ 4, the non-radiative decay is dominated by autoionization rather than predissociation. We examine the predicted NO + ion rotational state distributions generated by vibrational autoionization of g states and discuss applications of our model to achieve quantum state selection in the production of molecular ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1980

A study of the cleft region using synoptic ionospheric plasma data obtained by the polar orbiting satellites Aeros-B and Isis-2

The concentrations of O(+) and NO(+) in the dayside high-latitude cleft region of the ionosphere are investigated based on synoptic particle and plasma measurements obtained by the polar orbiting Aeros-B and Isis-2 satellites. At a time when the orbital planes of the satellites are almost at right angles to each other, three maxima in ion temperature are observed, with two of them accompanied by an increased electron temperature and electron density irregularities, and the density of the molecular ions NO(+) and O2(+) is found to increase at the expense of O(+) density. Results are discussed in terms of a theory relating perpendicular electric fields to oxygen atom reaction rates. Systematic analysis of the Aeros data base reveals 14 additional instances of O(+) to NO(+) conversion, with a large variety of forms and structures reflecting the complex structure and dynamics of the high-latitude dayside ionosphere.

Kist, R.↗
DOE OSTI2026

Conformational Isomerization of Imide Anions Governs Solvation and Transport in Water-in-Salt Electrolytes

The behavior of highly concentrated electrolytes departs radically from the dilute-solution theory, yet the molecular origin of this transformation remains unresolved. Here, we identify the conformational isomerization of molecular ions as a decisive, previously unrecognized control parameter governing structure and transport in crowded aqueous electrolytes. Across a series of fluorosulfonimide anions, we show that increasing concentration drives a collective shift from extended transoid to compact cisoid conformers, revealed by small-angle X-ray scattering, vibrational spectroscopy, pulsed-field gradient NMR, and molecular dynamics simulations. This conformational transition triggers a collapse of the hydrogen-bonded water network and the emergence of densely packed ionic domains with confined water, producing a qualitative change in Li+ transport from solvent-mediated diffusion to network-confined hopping. Anion size and asymmetry systematically tune the onset of this transition, demonstrating that molecular geometry dictates mesoscale organization and dynamics in the ion-rich regime. Our results establish ion conformation, not merely composition or coordination, as a fundamental thermodynamic variable in concentrated solutions, providing a chemical framework that unifies solvation structure and transport in water-in-salt electrolytes and suggesting new principles for designing dense ionic media.

Nguyen, Huong TD↗
DOE OSTI2023

Large Individual Ion FTICR Measurements from the Mid-1990s Using Reactions for Charge Determination Mass Spectrometry

This article discusses from a personal and present-day perspective the first studies of large highly charged individual molecular ions that were conducted using electrospray ionization (ESI) with Fourier transform ion cyclotron resonance (FTICR) MS in the mid-1990s. These studies are distinguished from current Charge Detection Mass Spectrometry (CDMS) research primarily by their use of individual ion charge state changes due to reactions. Here this work describes the key differences in technologies and methods with present CDMS, and the likely implications of these differences. I also comment on surprising individual ion behavior observed in some measurements involving increases in charge state, as well as their possible basis, and also briefly discuss the potential utility of the reaction-based mass measurement approach used in the context of what might more globally be referred to as ‘Charge Determination Mass Spectrometry’.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1984

Interactions between the orbiting Space Shuttle and the ionosphere

This paper presents an analysis of interactions between the Space Shuttle Orbiter and the ionosphere based on thermal plasma data obtained from a Spherical Retarding Potential Analyzer (SRPA) and a Langmuir Probe (LP) flown on the third Space Shuttle flight (STS-3) in March 1982. While previous work on spacecraft-plasma interactions has dealt with wake effects, the present work deals with effects that are seen in ram conditions that have not been previously discussed. One observation is a higher degree of plasma turbulence than has been reported from unmanned spacecraft measurements that manifests itself as a frequency component at 2.2 kHz in the SRPA signal. Also seen are unusually high number densities of what appear to be ions with a mass of at least 30 or 32 amu and a temperature in the range 2000-3000 K. Coincident with the enhanced molecular ion species, the temperature of the thermal electrons is seen elevated to above 5000 K. It is hypothesized that these measurements are evidence for a plasma instability resulting from the motion of the outgassing Orbiter through the ionosphere.

Siskind, D. E.↗
NASA NTRS1996

Products of Dissociative Recombination in the Ionosphere

SRI International undertook a novel experimental measurement of the product states formed by dissociative ro-combination (DR) of C2(+), NO(+), and N2(+) as a function of both electron energy and reactant ion vibrational level. For these measurements we used a recently developed experimental technique for measuring dissociation product distributions that allows both the branching ratios to be accurately determined and the electronic and ro-vibrational state composition of the reactant ions to be specified. DR is the dominant electron loss mechanism in all regions of the ionosphere. In this process, electron attachment to the molecular ion produces an unstable neutral molecule that rapidly dissociates.

Cosby, Philip↗
DOE OSTI2020

Spatial Profile and Beam Composition Measurements of the University of Wisconsin Inertial Electrostatic Confinement Laboratory Ion Guns

A custom designed and manufactured set of ion guns has been in use at the University of Wisconsin Inertial Electrostatic Confinement Laboratory for both beam fusion experiments and materials implantation experiments. For the first time, direct measurements have been made on the spatial profiles and the mass compositions of He and D ion beams produced by these guns. The results validate assumptions about the circular Gaussian spatial profiles for both He and D ion beams. Mass composition measurements of the He beam identified a pressure-dependent minimum impurity content of 15% N + . The D beam contained relative molecular ion fractions of 58% D 3 + , 32% D 2 + , and 10% D + with impurities of 15% to 20% D 2 O + . Finally, a new experimental platform, the Ion Beam and Source Analyzer was developed to perform these experiments on the ion guns used to irradiate candidate fusion materials.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1993

Equatorial ion composition, 140-200 km, based on Atmosphere Explorer E data

We have used in situ measurements of ion composition and horizontal winds, taken from equatorial orbiting Atmosphere Explorer E in eccentric orbit during 1975-1976 to investigate the bottomside ionosphere at altitudes 140-200 km. Representative daytime altitude profiles of ionization were stable against wide variations in horizontal wind patterns. Special features that sometimes appeared in the structured nightside ionization were apparent ion composition waves, intermediate layers of enhanced ionization, and ionization depletions similar to equatorial ionization bubbles. Apparent ion composition waves displayed a horizontal wave length of about 650 km. Enhanced layers of ionization appeared to be newly separated from the bottomside midnight F layer; its ions were primarily NO(+) and O2(+) without significant densities of metallic ions, an indication that metallic ions are not required to produce the layers at altitudes above 140 km. Equatorial ionization depletions were observed at lower altitudes than previously reported and displayed molecular ion depletions as well as O(+) depletions.

Miller, N. J.↗
NASA NTRS1989

Fast molecular shocks. I - Reformation of molecules behind a dissociative shock

The physical and chemical processes that operate in the cooling gas behind a fast, dissociative, single-fluid shock propagating in a dense interstellar cloud are discussed. The treatment extends previous theoretical work on fast molecular shocks by including the effects of the conversion of Ly-alpha photons into radiation of the two-photon continuum and into H2 Lyman band emission lines, the effects of CO photodissociation following line absorption, and the formation and destruction of molecules containing the elements nitrogen, silicon, and sulphur, and of the complex hydrocarbons. Abundance profiles for the molecular species of interest are presented. After molecular hydrogen begins to reform, by means of gas phase and grain surface processes, the neutral species OH, H2O, O2, CO, CN, HCN, N2, NO, SO, and SiO reach substantial abundances. The molecular ions HeH(+), OH(+), SO(+), CH(+), H2(+), and H3(+), are produced while the gas is still hot and partially ionized. Emissions from them provide a possible diagnostic probe of fast molecular shocks.

Neufeld, David A.↗
NASA NTRS1990

Unidentified ions in comets

Optical spectra were taken of comets Halley, West, and Brorsen-Metcalf in the wavelength region 3200 to 6400 A. These spectra were offset approximately 10(exp -5) to 10(exp -6) km tailward from the nucleus so that the features detected were all ions with the exception of a very small residual C2 emission at 5165 A. The full labeled tail spectrum of comet Halley is given. While most of the features detected are attributable to CO(+), H2O(+), CO2(+), CH(+), and OH(+), there are three moderately strong bands in the spectra of comets Halley and Brorsen-Metcalf which remain unidentified. These features were not detected in comet West. All three spectra in the 4800 to 5400 A region are presented, Brorsen-Metcalf is the gassiest of the three. The central wavelengths of the unidentified features are 4930, 5300, and 6000 A. In an effort to identify the ions responsible for these features as well as to confirm previous identifications, laboratory spectra of ions were compared with the comet spectra. H2O(+) and CO(+) are known to have extensive emission in the 4800 to 6200 A region. Therefore, the possibility that these unidentified features are due to H2O(+) and CO(+) was investigated. A search for the following bands was conducted: H2O(+) (11-0), H2O(+) (12-0), H2O(+) (13-1), CO(+) (1-1), and CO(+) (0-0). CO(+) (1-1) and CO(+) (0-0) were previously identified and are present in all the spectra examined. The H2O(+) (11-0) band was identified. Comparison of the H2O(+) (11-0) synthetic spectrum with comet Brorsen-Metcalf data is presented. The relative fluxes of the blended H2O(+) lines in the synthetic spectrum match those of the cometary data. After eliminating H2O(+) and CO(+) as significant contributors to the stronger unidentified features, spectra of ions which are not yet identified in the optical region of comets were compared to the data. These ions are NH(+), CS(+), and C2(+). None of these ions appears to be a significant contributor to the optical spectra of these three comets. In conclusion, H2O(+) (11-0) was unabiguously identified in cometary optical spectra. No other molecular ion for which there are laboratory spectra can explain the unidentified features found in the ion tails of comets Halley and Brorsen-Metcalf.

Engel, Lisa↗
NASA NTRS2001

Meteoric Ions in Planetary Ionospheres

Solar system debris, in the form of meteoroids, impacts every planet. The flux, relative composition and speed of the debris at each planet depends on the planet's size and location in the solar system. Ablation in the atmosphere evaporates the meteoric material and leaves behind metal atoms. During the ablation process metallic ions are formed by impact ionization. For small inner solar system planets, including Earth, this source of ionization is typically small compared to either photoionization or charge exchange with ambient molecular ions. For Earth, the atmosphere above the main deposition region absorbs the spectral lines capable of ionizing the major metallic atoms (Fe and Mg) so that charge exchange with ambient ions is the dominant source. Within the carbon dioxide atmosphere of Mars (and possibly Venus), photoionization is important in determining the ion density. For a heavy planet like Jupiter, far from the sun, impact ionization of ablated neutral atoms by impacts with molecules becomes a prominent source of ionization due to the gravitational acceleration to high incident speeds. We will describe the processes and location and extent of metal ion layers for Mars, Earth and Jupiter, concentrating on flagging the uncertainties in the models at the present time. This is an important problem, because low altitude ionosphere layers for the planets, particularly at night, probably consist predominantly of metallic ions. Comparisons with Earth will be used to illustrate the differing processes in the three planetary atmospheres.

Pesnell, W. D.↗
NASA NTRS1994

Factors controlling precision and accuracy in isotope-ratio-monitoring mass spectrometry

The performance of systems in which picomole quantities of sample are mixed with a carrier gas and passed through an isotope-ratio mass spectrometer system was examined experimentally and theoretically. Two different mass spectrometers were used, both having electron-impact ion sources and Faraday cup collector systems. One had an accelerating potential of 10kV and accepted 0.2 mL of He/min, producing, under those conditions, a maximum efficiency of 1 CO2 molecular ion collected per 700 molecules introduced. Comparable figures for the second instrument were 3 kV, 0.5 mL of He/min, and 14000 molecules/ion. Signal pathways were adjusted so that response times were <200 ms. Sample-related ion currents appeared as peaks with widths of 3-30 s. Isotope ratios were determined by comparison to signals produced by standard gases. In spite of rapid variations in signals, observed levels of performance were within a factor of 2 of shot-noise limits. For the 10-kV instrument, sample requirements for standard deviations of 0.1 and 0.5% were 45 and 1.7 pmol, respectively. Comparable requirements for the 3-kV instrument were 900 and 36 pmol. Drifts in instrumental characteristics were adequately neutralized when standards were observed at 20-min intervals. For the 10-kV instrument, computed isotopic compositions were independent of sample size and signal strength over the ranges examined. Nonlinearities of <0.04%/V were observed for the 3-kV system. Procedures for observation and subtraction of background ion currents were examined experimentally and theoretically. For sample/ background ratios varying from >10 to 0.3, precision is expected and observed to decrease approximately 2-fold and to depend only weakly on the precision with which background ion currents have been measured.

NASA Discipline Exobiology↗
NASA NTRS1991

Molecular origin of Io's fast sodium

Neutral sodium emissions encircling Jupiter exhibit an intricate and variable structure that is well matched by a simple loss process from Io's atmosphere. These observations imply that fast neutral sodium is created locally in the Io plasma torus, both near Io and as much as 8 hours downstream. Sodium-bearing molecules may be present in Io's upper atmosphere, where thay are ionized by the plasma torus and swept downstream. The molecular ions dissociate and dissociatively recombine on a short time scale, releasing neutral fragments into escape trajectories from Jupiter. This theory explains a diverse set of sodium observations, and it implies that molecular reactions (particularly electron impact ionization and dissociation) are important at the top of Io's atmosphere.

Schneider, Nicholas M.↗
NASA NTRS1992

Calculations of ion-molecule deuterium fractionation reactions involving HD

Gas-phase chemical models of deuterium fractionation in dense interstellar clouds utilize a small number of exothermic reactions to achieve fractionation. Although HD is a major repository of deuterium, it appears not to exchange deuterium with many molecular ions. Useful semiquantitative reasons have been given for the unusual lack of reactivity of exothermic ion-HD deuterium exchange systems, but quantum chemical studies are needed to understand these ideas in more detail and to determine if the lack of reactivity pertains at very low temperatures not studied in the laboratory, or whether tunneling can drive the reactions. Accordingly, the potential energy surfaces of three representative ion-molecule exchange reactions involving protonated ions and HD have been investigated with ab initio quantum chemical techniques. Our results generally confirm the semiquantitative picture as to which reactions are likely to occur and show that tunneling at low temperatures is unlikely to alter this picture.

Maluendes, Sergio A.↗
NASA NTRS2005

Ion Composition in Saturn's Plasma Environment: Early Results from the Cassini Plasma Spectrometer

Prior to Cassini s arrival at Saturn, most of what was known about the composition of the plasma in Saturn s environment was derived from limited measurements by Pioneer 11 and Voyager 1 and 2 in 1979-1981[1-3]. The measurements reported here were made by the Cassini Plasma Spectrometer (CAPS) [4] during the first two Cassini orbits, including the closest approach to Saturn and the rings during the tour, and a close flyby of Titan. The CAPS instrument resolves ion energy/charge from 1 V to 50 kV and ion mass/charge from 1 to approx.100 amu/e, and it measures electron energy from 1 eV to 28 keV. Initial composition measurements of Saturn s magnetosphere show that protons dominate outside approx.8 R(sub s), while inside this radius the plasma is dominated by a mix of water-derived ions and N(+). Over the A and B rings a plasma layer is observed composed of O2(+) and O(+) . The close passage near Titan shows a rich network of both positive and negative molecular ions. We report preliminary analysis of these and other composition findings.

Reisenfeld, D. B.↗
DOE OSTI2021

Experimental studies on photoabsorption by endohedral fullerene ions with a focus on Xe@C 60 + confinement resonances

A brief overview on the status of experimental investigations into photoionization and fragmentation of fullerenes and endohedral fullerenes by absorption of a single short-wavelength photon is presented. The focus of this paper is on the endohedral Xe@C 60 + molecular ion in which a xenon atom is centrally encapsulated inside a C$^{+}_{60}$ fullerene cage. Confinement resonances that result from the interference of Xe photoelectron matter waves emerging from the C$^{+}_{60}$ cavity were studied by exposing Xe@C 60 + ions to synchrotron radiation of 60 to 150 eV energy which is the region of the well-known giant atomic Xe 4d excitation resonance. Photoions Xe@C n q+ (with final charge states q = 2,3,4 of the product ions and numbers of carbon atoms left in the cage) were recorded as a function of photon energy and cross sections for the individual reaction channels were determined. In addition to previous work, new final channels (q = 2; n = 60, 58 and q = 4; n = 58, 56) were observed, and thus, about 70% of the oscillator strength expected for the encapsulated Xe atom in the investigated energy range could be recovered. The present results establish the first and, so far, only conclusive experimental observation of confinement resonances in an endohedral fullerene. The data are in remarkable agreement with relativistic R-matrix calculations that accompanied the previous experimental work.

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

Open-Shell Tensor Hypercontraction

The extension of least-squares tensor hypercontracted second- and third-order Møller–Plesset perturbation theory (LS-THC-MP2 and LS-THC-MP3) to open-shell systems is an important development due to the scaling reduction afforded by THC and the ubiquity of molecular ions, radicals, and other open-shell reactive species. The complexity of wavefunction-based quantum-chemical methods such as Møller–Plesset and coupled cluster theory is reflected in the steep scaling of the computational costs with the molecular size. The least-squares tensor hypercontraction (LS-THC) method is an efficient, single-step factorization for the two-electron integral tensor but can also be used to factorize the double excitation amplitudes, leading to significant scaling reduction. Herein we extend this promising method to open-shell variants of LS-THC-MP2 and -MP3 by using diagrammatic techniques and explicit spin summation. The accuracy of the resulting methods for open-shell species is benchmarked on standard test systems such as regular alkanes as well as realistic systems involving bond breaking, radical stabilization, and other effects. We find that open-shell LS-THC-MPn methods exhibit errors highly comparable to those produced by closed-shell LS-THC-MPn and are highly insensitive to particular chemical interactions, geometries, or even moderate spin contamination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗