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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Probing the self-ionization of liquid water with ab initio deep potential molecular dynamics

The chemical equilibrium between self-ionized and molecular water dictates the acid–base chemistry in aqueous solutions, yet understanding the microscopic mechanisms of water self-ionization remains experimentally and computationally challenging. Herein, Density Functional Theory (DFT)–based deep neural network (DNN) potentials are combined with enhanced sampling techniques and a global acid–base collective variable to perform extensive atomistic simulations of water self-ionization for model systems of increasing size. The explicit inclusion of long-range electrostatic interactions in the DNN potential is found to be crucial to accurately reproduce the DFT free energy profile of solvated water ion pairs in small (64 and 128 H 2 O) cells. The reversible work to separate the hydroxide and hydronium to a distance S is found to converge for simulation cells containing more than 500 H 2 O, and a distance of ∼ 8 Å is the threshold beyond which the work to further separate the two ions becomes approximately zero. The slow convergence of the potential of mean force with system size is related to a restructuring of water and an increase of the local order around the water ions. Calculation of the dissociation equilibrium constant illustrates the key role of long-range electrostatics and entropic effects in the water autoionization process.

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

Enhancement of reactive oxygen species production by ultra-short electron pulses

The development of laser-driven accelerators-on-chip has provided an opportunity to miniaturize devices for electron radiotherapy delivery. Laser-driven accelerators produce highly time-compressed electron pulses, on the 100 fs to 1 ps scale. This delivers electrons at high peak power yet low average beam current compared with conventional delivery devices, which generate pulses of approximately 3 µs. The biophysical effects of this time structure, however, are unclear. Here, we use a Monte Carlo simulation approach to explore the effects of the electron beam time structure on the production of reactive oxygen species (ROS) in water. Our results show a power law increase in the generation of hydroxyl ions per deposited electron with decreasing pulse length over the pulse length range of 10 µs to 100 fs. Similar trends were observed for hydrogen peroxide, superoxide, hydroperoxyl, hydronium and solvated electrons. In practical terms, this indicates a fourfold increase in the efficiency of free radical production for sub-picosecond pulses, relative to that of conventional microsecond pulses, for the same number of deposited electrons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Hydration and reaction mechanisms on sodium silicate glass surfaces from molecular dynamics simulations with reactive force fields

Recent development of reactive force fields have enabled molecular dynamics simulations of interactions between silicate glasses and water at the atomistic scale. While multicomponent silicate glasses encompass a wide variety of compositions and properties, one common structural feature in these glasses is the combination of the network structure that is made up of silica tetrahedra linked through corner sharing interspersed with network modifiers like alkali and alkaline-earth ions that break up the Si–O–Si linkages by forming nonbridging oxygen. In reactions with water, ion exchange between alkali ions in the glass and proton or hydronium in the solution, as well as hydrolysis reaction of the Si–O–Si linkages and subsequent silanol formation, is observed and well documented. Furthermore, we have used a set of recently developed reactive force field to investigate the reactions between water and the surfaces of silica and sodium silicate glasses of different compositions for reactions up to 8 nanoseconds. Our results indicate sodium leaching into water and diffusion of water molecules up to 25 Å into the glass surface. We examined the structural and compositional changes inside the glass and around the diffused ions and use these to explain the rates of silanol formation at the surface. We also observed proton transport in the glass which has an indirect influence on the silanol formation rates. While the surface of the glass was rough to start with, it undergoes further modification into a hydrated gel-like structure in the glass for up to 5 Å in the higher alkali containing glasses. It was found that the leached sodium ions remain close to the interface and that fragments of silicate network from the surface is capable of dislodging from the bulk glass and enter the aqueous solution. These simulations thus provide insights into the formation and structure of an alteration layers commonly observed in multicomponent silicate glasses corroded in aqueous solutions.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Solvent molecules form surface redox mediators in situ and cocatalyze O 2 reduction on Pd

Solvent molecules influence the reactions of molecular hydrogen and oxygen on palladium nanoparticles. Organic solvents activate to form reactive surface intermediates that mediate oxygen reduction through pathways distinct from reactions in pure water. Kinetic measurements and ab initio quantum chemical calculations indicate that methanol and water cocatalyze oxygen reduction by facilitating proton-electron transfer reactions. Methanol generates hydroxymethyl intermediates on palladium surfaces that efficiently transfer protons and electrons to oxygen to form hydrogen peroxide and formaldehyde. Formaldehyde subsequently oxidizes hydrogen to regenerate hydroxymethyl. Water, on the other hand, heterolytically oxidizes hydrogen to produce hydronium ions and electrons that reduce oxygen. These findings suggest that reactions of solvent molecules at solid-liquid interfaces can generate redox mediators in situ and provide opportunities to substantially increase rates and selectivities for catalytic reactions.

Adams, Jason S.↗
DOE OSTI2022

Direct and Sensitive Electrochemical Evaluation of Pramipexole Using Graphitic Carbon Nitride (gCN) Sensor

Pramipexole (PMXL) belongs to the benzothiazole class of aromatic compounds and is used in treating Parkinson’s disease; however, overdosage leads to some abnormal effects that could trigger severe side effects. Therefore, it demands a sensitive analytical tool for trace level detection. In this work, we successfully developed an electrochemical sensor for the trace level detection of PMXL, using the voltammetric method. For the analysis, graphitic carbon nitride (gCN) was opted and synthesized by using a high-temperature thermal condensation method. The synthesized nanoparticles were employed for surface characterization, using transmission electron microscopy (TEM), X-ray diffraction (XRD), and atomic force microscopy (AFM) techniques. The electrochemical characterization of the material was evaluated by using the electrochemical impedance spectroscopy (EIS) technique to evaluate the solution–electrode interface property. The cyclic voltammetry (CV) behavior of PMXL displayed an anodic peak in the forward scan, indicating that PMXL underwent electrooxidation, and an enhanced detection peak with lower detection potential was achieved for gCN-modified carbon paste electrode (gCN·CPE). The influence of different parameters on the electrochemical behavior was analyzed, revealing the diffusion governing the electrode process with an equal number of hydronium ions and electron involvement. For the fabricated gCN·CPE, good linearity range was noticed from 0.05 to 500 µM, and a lower detection limit (L D ) of 0.012 µM was achieved for the selected concentration range (0.5 to 30 µM). Selectivity of the electrode in PMXL detection was investigated by conducting an interference study, while the tablet sample analysis demonstrates the sensitive and real-time application of the electrode. The good recovery values for the analysis illustrate the efficiency of the electrode for PMXL analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Product ion distributions using H 3 O + proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS): mechanisms, transmission effects, and instrument-to-instrument variability

Abstract. Proton-transfer-reaction mass spectrometry (PTR-MS) using hydronium ion (H3O+) ionization is widely used for the measurement of volatile organic compounds (VOCs) both indoors and outdoors. H3O+ ionization, as well as the associated chemistry in an ion–molecule reactor, is known to generate product ion distributions (PIDs) that include other product ions besides the proton-transfer product. We present a method, using gas-chromatography pre-separation, for quantifying PIDs from PTR-MS measurements of nearly 100 VOCs of different functional types including alcohols, ketones, aldehydes, acids, aromatics, organohalides, and alkenes. We characterize instrument configuration effects on PIDs and find that reactor reduced electric field strength (E/N), ion optic voltage gradients, and quadrupole settings have the strongest impact on measured PIDs. Through an interlaboratory comparison of PIDs measured from calibration cylinders, we characterized the variability of PID production from the same model of PTR-MS across seven participating laboratories. Product ion variability was generally smaller (e.g., < 20 %) for ions with larger contributions to the PIDs (e.g., > 0.30) but less predictable for product ions formed through O2+ and NO+ reactions. We present a publicly available library of H3O+ PTR-MS PIDs that will be updated periodically with user-provided data for the continued investigation into instrument-to-instrument variability of PIDs.

Link, Michael F. (ORCID:0000000218412455)↗
DOE OSTI2025

Positive and Negative Ion CIMS Measurements, SGP, May-June 2024

The negative ion measurements were taken using two LTOF-CIMS with two different nitrate inlets. The data labeled Aerodyne_Inlet used an Aerodyne nitrate inlet. Data labeled PCC used a custom transverse inlet. The positive ion measurements were taken using one LTOF-CIMS with hydronium as an ionization reagent using a custom transverse inlet with an inlet voltage difference of 700 V. See https://doi.org/10.1021/acs.jpca.2c01672 for more information. Peaks were autofit using tofware. Positive ion data is published in the form of peak signal/reagent signal. Data files of peak signal/reagent signal for the two mass spectrometers for the negative ion measurements are separate. Concentrations of H2SO4 are combined into one file. When measurements were overlapping, measurements from the Aerodyne nitrate inlet were used.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1976

Ion composition in a noctilucent cloud

Ion composition at mesospheric altitudes was measured and compared between high and mid-latitude sites under summer daytime conditions. Rocket-borne measurements were made with pumped quadrupole ion mass spectrometers. The mid-latitude data were obtained at Wallops Island, Virginia on June 30, 1973, at 1510 LMT. Large quantities of hydronium cluster ions were observed through 109+, with maximum concentrations at 55+ and 73+. Also, cluster ions of nitric oxide were observed through 84+. The high latitude launch occurred at Kiruna, Sweden on August 2, 1973, at 0700 LMT following visual sighting of a noctilucent cloud on the prior evening. The data near mesopause shows cluster ions, but also a preponderance of heavy ions between 90 and 145 AMU, with groupings 18 AMU apart but unrelated to the more typical cluster ions. One possible set of consistent identifications leads to iron and iron oxide hydrates. These results may suggest the presence of metallic particulates and ions which form hydrated clusters ions.

Goldberg, R. A.↗
NASA NTRS1977

Ion composition in a noctilucent cloud region

Ion composition at mesospheric altitudes was measured at high-latitude (Kiruna, Sweden) and mid-latitude (Wallops Island, Virginia) sites under summer daytime conditions, using two sets of rocket measurements both made with pumped quadrupole ion mass spectrometers. Cluster ions of hydronium and of nitric oxide were observed at midlatitudes, while, in addition to these cluster ions, a preponderance of heavy ions between 90 and 145 amu, was observed at high latitudes. These latter results may suggest the presence of metallic particles and ions which form hydrated cluster ions within the noctilucent cloud region.

Goldberg, R. A.↗
NASA NTRS1980

Electron-temperature dependence of dissociative recombination of electrons with CO(+)-(CO)n-series ions

A microwave afterglow mass spectrometer apparatus is used to determine the dependence on electron temperature T sub e of the recombination coefficients alpha sub n of the dimer and trimer ions of the series CO+.(CO) sub n. It is found that alpha sub 1 = (1.3 + or - 0.3)x 0.000001 (T sub e(K)/300) to the -0.34; and alpha sub 2 = (1.9 + or - 0.4)x 0.000001 (T sub e(K)/300) to the -0.33 cu cm/sec. These dependences on T sub e are quite different from those obtained previously for polar-cluster ions of the hydronium and ammonium series but are similar to that for simple diatomic ions.

Whitaker, M.↗
NASA NTRS1981

Electron-temperature dependence of dissociative recombination of electrons with CO/+/./CO/n-series ions

The dependence on electron temperature of the coefficients for electron recombination with molecular cluster ions of the carbon monoxide series, CO(+).(CO)n, is determined. A microwave discharge lasting approximately 0.1 msec was applied in 5-20 Torr neon containing a few tenths percent CO in an afterglow mass spectrometer apparatus, and the time histories of the various afterglow ions were measured. Expressions for the dependence of the recombination coefficients of the dimer and trimer ions CO(+).CO and CO(+).(CO)2 are obtained which are found to be significantly different from those previously obtained for hydronium and ammonium series polar cluster ions, but similar to those of simple diatomic ions.

Whitaker, M.↗
NASA NTRS1982

The cometary atmosphere and its interaction with the solar wind

The present state of knowledge of cometary atmospheres and their interaction with the solar winds is assessed. Current models of the magnetospheres and ionospheres of comets are based on either an atmospheric chemistry approach, minimizing the effects of atmospheric dynamics and thermodynamics, while the other method takes the exact opposite viewpoint and roles and significance are reversed. A major difficulty in completing the models is a lack of data on the chemical composition of the cometary nucleus, although UV observations have revealed the H, C, O, and S elemental abundance ratios. It is suggested that further studies of collisional ionization by energetic electrons be performed to characterize processes in the cometary atmosphere. Hydronium may be the dominat molecule in the inner coma, if the assumption that the ionosphere is a magnetic field-free cavity separated from the solar wind by an unyielding tangential discontinuity surface is accurate. Particular observations and theoretical attention are recommended for the solar wind interaction in the intermediate range, i.e., 2.5-5 AU, when the cometary atmosphere develops.

Mendis, D. A.↗
NASA NTRS1995

Ca-Rich Carbonate Melts: A Regular-Solution Model, with Applications to Carbonatite Magma + Vapor Equilibria and Carbonate Lavas on Venus

A thermochemical model of the activities of species in carbonate-rich melts would be useful in quantifying chemical equilibria between carbonatite magmas and vapors and in extrapolating liquidus equilibria to unexplored PTX. A regular-solution model of Ca-rich carbonate melts is developed here, using the fact that they are ionic liquids, and can be treated (to a first approximation) as interpenetrating regular solutions of cations and of anions. Thermochemical data on systems of alkali metal cations with carbonate and other anions are drawn from the literature; data on systems with alkaline earth (and other) cations and carbonate (and other) anions are derived here from liquidus phase equilibria. The model is validated in that all available data (at 1 kbar) are consistent with single values for the melting temperature and heat of fusion for calcite, and all liquidi are consistent with the liquids acting as regular solutions. At 1 kbar, the metastable congruent melting temperature of calcite (CaCO3) is inferred to be 1596 K, with (Delta)bar-H(sub fus)(calcite) = 31.5 +/- 1 kJ/mol. Regular solution interaction parameters (W) for Ca(2+) and alkali metal cations are in the range -3 to -12 kJ/sq mol; W for Ca(2+)-Ba(2+) is approximately -11 kJ/sq mol; W for Ca(2+)-Mg(2+) is approximately -40 kJ/sq mol, and W for Ca(2+)-La(3+) is approximately +85 kJ/sq mol. Solutions of carbonate and most anions (including OH(-), F(-), and SO4(2-)) are nearly ideal, with W between 0(ideal) and -2.5 kJ/sq mol. The interaction of carbonate and phosphate ions is strongly nonideal, which is consistent with the suggestion of carbonate-phosphate liquid immiscibility. Interaction of carbonate and sulfide ions is also nonideal and suggestive of carbonate-sulfide liquid immiscibility. Solution of H2O, for all but the most H2O-rich compositions, can be modeled as a disproportionation to hydronium (H3O(+)) and hydroxyl (OH(-)) ions with W for Ca(2+)-H3O(+) (approximately) equals 33 kJ/sq mol. The regular-solution model of carbonate melts can be applied to problems of carbonatite magma + vapor equilibria and of extrapolating liquidus equilibria to unstudied systems. Calculations on one carbonatite (the Husereau dike, Oka complex, Quebec, Canada) show that the anion solution of its magma contained an OH mole fraction of (approximately) 0.07, although the vapor in equilibrium with the magma had P(H2O) = 8.5 x P(CO2). F in carbonatite systems is calculated to be strongly partitioned into the magma (as F(-)) relative to coexisting vapor. In the Husereau carbonatite magma, the anion solution contained an F(-) mole fraction of (approximately) 6 x 10(exp -5).

Treiman, Allan H.↗
NASA NTRS2004

Formation and Stability of Radiation Products in Europa's Icy Shell

Spectra of Europa reveal a surface dominated by water-ice along with hydrated materials and minor amounts of SO2, CO2, and H2O2. Jovian magnetospheric ions (protons, sulfur, and oxygen) and electrons produce significant chemical modifications of the surface on time scales of a few years at micrometer depths. Our laboratory studies examine the formation and stability of radiation products in H2O-rich ices relevant to Europa. Infrared (IR) spectra of ices before and after irradiation reveal the radiation destruction of molecules and the formation of products at 86 - 132 K. In addition, spectra of ices during warming track thermal evolution due to chemical changes and sublimation processes. IR-identified radiation products in 86 - 132 K irradiated H2O + SO2 ices are the bisulfate ion, HSO4(-), sulfate ion, SO4(2-) and the hydronium ion, H3O(+). Warming results in the formation of a residual spectrum similar to liquid sulfuric acid, H2SO4, for H2O:SO2 ratios of 30:1, whereas hydrated sulfuric acid, H2SO4 4 H2O, forms for ratios of 30:1. Radiation products identified for irradiated H2O + H2S ices at 86 K are H2S2 and SO2. When irradiated at 110 and 132 K, ices with H2O:H2S ratios if either 3:1 or 30:1 show the formation of H2SO4 4 H2O on warming to 175 K. We have also examined the radiation stability of H2SO4. Addition of CO2 to H2O + SO2 ices results in the formation of CO3 at 2046 cm (sup -1) (4.89 m). This is the strongest band from a carbon-containing product in the mid-IR spectral region, and it is also seen when either pure CO2 or H2O + CO2 ice is irradiated. Experiments with CH4 added to H2O + SO2 + CO2 ices addressed the question of methane's use as a marker of methanogens in an irradiated ice environment. New results on the near-IR spectrum of pure H2O2 will be included in this presentation. Interpretations of near-IR water bands, with H2O2 present, will be discussed. Irradiations of H2O2 and H2O + H2O2 mixtures, to examine the possibility of O2 and O3 formation, are currently under investigation and new results will be discussed.

Moore, M. H.↗
NASA NTRS2004

Photoionization in Ultraviolet Processing of Astrophysical Ice Analogs at Cryogenic Temperatures

Two recent experimental studies have demonstrated that amino acids or amino acid precursors are generated when astrophysical ice analogs are subjected to ultraviolet (UV) irradiation at cryogenic temperatures. Understanding the complete phenomenology of photoprocessing is critical to elucidating chemical reaction mechanisms that can function within an ice matrix under very cold conditions. Pushing beyond the much better characterized study of photolytic dissociation of chemical bonds through electronic excitation, this work explored the ability of UV radiation present in the interstellar medium to ionize small molecules embedded in ices. Quantum chemical calculations, including bulk solvation effects, were used to study the ionization of hydrogen (H2), water, and methanol (CH3OH) bound in small clusters of water. Ionization potentials were found to be much smaller in the condensed phase than in the gas phase; even a small cluster can account for large changes in the ionization potentials in ice, as well as the known formation of an OH--H3O+ pair in the case of H2O photoionization. To gauge the impact of photoionization on subsequent grain chemistry, the reaction between OH and CO in the presence of H3O+ was studied and compared with the potential energy surface without hydronium present, which is relevant to chemistry following photolysis. The differences indicate that the reaction is somewhat more likely to proceed to products (H + CO2) in the case of photoionization.

Woon, David E.↗
NASA NTRS2006

Theoretical Modeling of Formic Acid (HCOOH), Formate (HCOO(-)), and Ammonia (NH(4)) Vibrational Spectra in Astrophysical Ices

Ions embedded in icy grain mantles are thought to account for various observed infrared spectroscopic features, particularly in certain young stellar objects. The dissociation of formic acid (HCOOH) in astrophysical ices to form the formate ion (HCOO(-)) was modeled with density functional theory cluster calculations. Like isocyanic acid (HOCN), HCOOH was found to spontaneously deprotonate when sufficient water is present to stabilize charge transfer complexes. Both ammonia and water can serve as proton acceptors, yielding ammonium (NH4(+)) and hydronium (H3O(+)) counterions. Computed frequencies of weak infrared features produced by stretching and bending modes in both HCOO(-) and HCOOH were compared with experimental and astronomical data. Our results confirm laboratory assignments that a band at 1381 cm(exp -1) can be attributed to the CH bend in either HCOO(-) or HCOOH, but a band at 1349 cm(exp -1) corresponds to CO stretching in HCOO(-). Another feature at 1710 cm(exp -1) (5.85 m) can possibly be assigned to a CO stretching mode in HCOOH, as suggested by experiment, but the agreement is less satisfactory. In addition, we examine and analyze spectroscopic features associated with NH+4, both as a counterion to HCOO(-) or OCN(-) and in isolation, in order to compare with experimental and astronomical data in the 7 m region.

Park, Jin-Young↗
NASA NTRS2005

The Rio Tinto Basin, Spain: Mineralogy, Sedimentary Geobiology, and Implications for Interpretation of Outcrop Rocks at Meridiani Planum, Mars

Exploration by the NASA rover Opportunity has revealed sulfate- and hematite-rich sedimentary rocks exposed in craters and other surface features of Meridiani Planum, Mars. Modern, Holocene, and Plio-Pleistocene deposits of the Rio Tinto, southwestern Spain, provide at least a partial environmental analog to Meridiani Planum rocks, facilitating our understanding of Meridiani mineral precipitation and diagenesis, while informing considerations of martian astrobiology. Oxidation, thought to be biologically mediated, of pyritic ore bodies by groundwaters in the source area of the Rio Tinto generates headwaters enriched in sulfuric acid and ferric iron. Seasonal evaporation of river water drives precipitation of hydronium jarosite and schwertmannite, while (Mg,Al,Fe(sup 3+))-copiapite, coquimbite, gypsum, and other sulfate minerals precipitate nearby as efflorescences where locally variable source waters are brought to the surface by capillary action. During the wet season, hydrolysis of sulfate salts results in the precipitation of nanophase goethite. Holocene and Plio-Pleistocene terraces show increasing goethite crystallinity and then replacement of goethite with hematite through time. Hematite in Meridiani spherules also formed during diagenesis, although whether these replaced precursor goethite or precipitated directly from groundwaters is not known. The retention of jarosite and other soluble sulfate salts suggests that water limited the diagenesis of Meridiani rocks. Diverse prokaryotic and eukaryotic microorganisms inhabit acidic and seasonally dry Rio Tinto environments. Organic matter does not persist in Rio Tinto sediments, but biosignatures imparted to sedimentary rocks as macroscopic textures of coated microbial streamers, surface blisters formed by biogenic gas, and microfossils preserved as casts and molds in iron oxides help to shape strategies for astrobiological investigation of Meridiani outcrops.

Fernandez-Remolar, David C.↗
NASA NTRS2011

Ion-Ice Astrochemistry: Barrierless Low-Energy Deposition Pathways to HCOOH, CH3OH, and CO2 on Icy Grain Mantles from Precursor Cations

A new family of very favorable reaction pathways is explored involving the deposition of ions on icy grain mantles with very low energies. Quantum chemical cluster calculations at the MP2/6-31+G** level in 4H2O clusters and at the B3LYP/6-31+G** level in 17H2O clusters indicate that HCO+ and CH3 + are able to react spontaneously with one of the water molecules in the cluster to form protonated formic acid (HCOOH2 +) and protonated methanol (CH3OH2 +), respectively. It is furthermore found that these initial adducts spontaneously transfer their excess protons to the cluster to form neutral formic acid and methanol, plus solvated hydronium, H3O+. In the final case, if a CO molecule is bound to the surface of the cluster, OH+ may react with it to form protonated carbon dioxide (HCO2 +), which then loses its proton to yield CO2 and H3O+. In the present model, all of these processes were found to occur with no barriers. Discussion includes the analogous gas phase processes, which have been considered in previous studies, as well as the competitive abstraction pathway for HCO(+) + H2O.

Woon, David E.↗