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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 NTRS2018

Hybrid Reduced Order Model for N2-N2 Interactions for Application to Dissociation and Energy Transfer Processes

Recent work in the aerothermodynamics community has focused on the development of reduced-order models for thermo-chemical non-equilibrium which avoid the restrictive assumptions of multi-temperature models and the prohibitive cost associated with State-to-State (StS) models. In the present work, this is accomplished by lumping energy states together and assuming groups of states are roughly in equilibrium. As a result, the non-equilibrium behavior of a gas can be captured at a reduced computational cost from a full StS simulation. In this work, we present a hybrid grouping model for studying energy transfer and dissociation in a mixture of nitrogen molecules due to N2-N2 reactions. This is accomplished by making use of a grouping strategy informed by data from the N2-N StS kinetic data. However, due to the massive computational cost associated with constructing StS data for the N2-N2 system, the kinetic data for the hybrid grouping model are calculated using the quasi-classical trajectory (QCT) method by sampling states for trajectory within the groups. This general framework is called the Maximum-Entropy Quasi-Classical Trajectory (ME-QCT) method. The primary challenge associated with this method is that rates for reverse grouped reactions cannot be obtained through detailed balance at a group level, due to the variation of group internal temperatures. To construct the full model for N2-N2 grouped kinetics using the ME-QCT method, detailed balance is invoked at the microscopic level, allowing for the calculation of the full kinetic data from QCT. Results will be presented using the full ME-QCT model for the N2-N2 system in an isothermal and isochoric reactor simulation. In addition, simple CFD test cases for a one-dimensional standing shock and for a quasi-one-dimensional nozzle will be used for demonstration of the ME-QCT method. This method allows for the calculation of non-equilibrium behavior for the N2-N2 system without the prohibitive cost of a full StS simulation. Moreover, it enables the construction of a unified model for the dissociating and recombining non-equilibrium flows.

nonequilibrium modeling↗
NASA NTRS1986

A model of Comet P/Giacobini-Zinner

A computer model of Comet P/Giacobini-Zinner is presented which contains photoprocesses, gas-phase chemical kinetics, energy balance, multifluid hydrodynamics with a transition to free molecular flow, and solar wind interaction. Recently the physics for electrons in the model has been improved by including electron impact ionization and dissociation and separately accounting for electron energetics. Electron heating and cooling mechanisms include photoprocesses, recombination processes, inelastic and elastic collisions with heavy molecules, and expansion cooling. The model incorporates an internally consistent interaction of the solar wind with the coma gas using the axisymmetric ideal fluid dynamic equations. The nuclear size and composition have been chosen to make the calculations relevant to the September 11, 1985 International Cometary Explorer (ICE) encounter with Comet P/Giacobini-Zinner. Model profiles of the temperature, velocity, and number density of the electrons are in good agreement with measurements along ICE's trajectory. The results indicate the probe passed through a region of the coma at the onset of the plasma tail.

Boice, D. C.↗
NASA NTRS1976

A simple approach to metal hydride alloy optimization

Certain metals and related alloys can combine with hydrogen in a reversible fashion, so that on being heated, they release a portion of the gas. Such materials may find application in the large scale storage of hydrogen. Metal and alloys which show high dissociation pressure at low temperatures, and low endothermic heat of dissociation, and are therefore desirable for hydrogen storage, give values of the Hildebrand-Scott solubility parameter that lie between 100-118 Hildebrands, (Ref. 1), close to that of dissociated hydrogen. All of the less practical storage systems give much lower values of the solubility parameter. By using the Hildebrand solubility parameter as a criterion, and applying the mixing rule to combinations of known alloys and solid solutions, correlations are made to optimize alloy compositions and maximize hydrogen storage capacity.

Lawson, D. D.↗
NASA NTRS1989

Dissociative recombination in interstellar clouds

Molecular ions play a significant role in the chemistry and evolution of interstellar molecular clouds, even though these regions are overwhelmingly neutral. The dissociative recombination (DR) process governs the abundances of many of these ions and of related neutral species. The gas-phase ion-molecule chemistry of the simplest species is summarized, with emphasis on those problems which are most sensitive to uncertain rates or product branching ratios of DR processes. Examples of the kinds of information needed about DR processes are presented. The importance of the H3(+) ion and prospects for its direct observation are discussed.

Black, John H.↗
DOE OSTI2020

Heterolytic Hydrogen Activation: Understanding Support Effects in Water–Gas Shift, Hydrodeoxygenation, and CO Oxidation Catalysis

Identifying the role of oxide supports in transition metal catalysis is critical toward our understanding of heterogeneous catalysis. The water-gas shift (WGS) reaction is a prototypical example where oxide support dictates catalytic activity, yet the cause for this remains uncertain. Herein, we show that a single descriptor—the equilibrium constant for hydroxyl formation—relates the WGS turnover frequency across disparate oxide supports. The dissimilar equilibrium constant, or oxophilicity, between early and late transition metals exemplify the utility of metal-support interfacial sites to circumvent adsorption-energy scaling restrictions, thereby providing bifunctional gains for the WGS reaction class. In relation, the equilibrium constant for hydroxyl formation is equivalent to the equilibrium constant for the formal heterolytic dissociation of hydrogen, and therefore, reflects the ability of the metal-support interface to participate in hydrogen heterolysis. The ubiquitous coexistence, yet divergent chemical behavior of homo- and heterolytically activated hydrogen renders oxide support identity central toward our understanding of hydrogenation catalysis. This work was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences and performed at the Environmental Molecular Sciences Laboratory in (EMSL), which is a DOE Office of Science User Facility located at the Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle. Computational resources were provided by a user proposal at the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility. N.N. would like to thank Oliver Y. Gutierrez for critical feedback during the final stage of manuscript preparation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1974

Extreme ultraviolet photodissociative excitation of molecular oxygen

Photodissociation processes in molecular oxygen occurring in the wavelength range from 500 to 900 A, investigated through observations of the resulting atomic fluorescence radiation, are reported. The dispersed radiation from a continuous light source was used to excite the gas, and the resulting fluorescence radiation was observed in the ultraviolet and infrared. The results obtained are compared with the dissociation cross sections derived by Matsunaga and Watanabe (1967).

Carlson, R. W.↗
NASA NTRS1981

On the role of vibrational excitation in dissociative recombination

An improved physical model of dissociative recombination is presented and applied to experimental data on the temperature dependence of rate coefficients for the rare-gas and atmospheric-gas ions. It is shown that in the charge neutralisation of the rare-gas dimer ions, autoionisation plays an important role (at least in comparison with the atmospheric-gas ions) and contributes to the fast fall-off in the rate coefficient with vibrational excitation observed in shock tube studies. Numerical estimates of the observed fall-off in rate coefficient with increasing vibrational excitation are also presented.

Cunningham, A. J.↗
NASA NTRS1993

A shock origin for interstellar H2O masers

We present a comprehensive model for the powerful H2O masers observed in starforming regions. In this model the masers occur behind dissociative shocks propagating in dense regions. This paper focuses on high-velocity dissociative shocks in which the heat of H2 reformation on dust grains maintains a large column of 300 - 400 K gas, where the chemistry drives a considerable fraction of the oxygen not in CO to form H2O. The H2O column densities, the hydrogen densities, and the warm temperatures produced by these shocks are sufficiently high to enable powerful maser action, where the maser is excited by thermal collisions with H atoms and H2 molecules. A critical ingredient in determining the shock structure is the magnetic pressure, and the fields required by our models are in agreement with recent observations. The observed brightness temperatures are the result of coherent velocity regions which have dimensions in the shock plane that are five to 50 times the postshock thickness.

Hollenbach, David↗
DOE OSTI2022

Annihilating Actinic Photochemistry of the Pyruvate Anion by One and Two Water Molecules

Photochemical behaviors of pyruvic acid in multiple phases have been extensively studied, while those of its conjugate base, the pyruvate anion (CH 3 COCOO – , PA – ) are less understood and remain contradictory in gaseous versus aqueous phases. Here in this article, we report a joint experimental and theoretical study combining cryogenic, wavelength-resolved negative ion photoelectron spectroscopy (NIPES) and high-level quantum chemical computations to investigate PA – actinic photochemistry and its dependence on microsolvation in the gas phase. PA – ·nH 2 O (n = 0–5) clusters were generated and characterized, with their low-lying isomers identified. NIPES conducted at multiple wavelengths across the PA – actinic regime revealed the PA – photochemistry extremely sensitive to its hydration extent. While bare PA – anions exhibit active photoinduced dissociations that generate the acetyl (CH 3 CO – ), methide (CH 3 – ) anions, their corresponding radicals, and slow electrons, one single attached water molecule results in significant suppression with a subsequent second water being able to completely block all dissociation pathways, effectively annihilating all PA – photochemical reactivities. Further, the underlying dissociation mechanisms of PA – ·nH 2 O (n = 0–2) clusters are proposed involving nπ* excitation, dehydration, decarboxylation, and further CO loss. Since the photoexcited dihydrate does not have sufficient energy to overcome the full dehydration barrier before PA – could fragmentate, the PA – dissociation pathway is completely blocked, with the energy most likely released via loss of one water and internal electronic and vibrational relaxations. The insight unraveled in this work provides a much-needed critical link to connect the seemingly conflicting PA – actinic chemistry between the gas and condensed phases.

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

Using a multistate mapping approach to surface hopping to predict the ultrafast electron diffraction signal of gas-phase cyclobutanone

Using the recently developed multistate mapping approach to surface hopping (multistate MASH) method combined with SA(3)-CASSCF(12,12)/aug-cc-pVDZ electronic structure calculations, the gas-phase isotropic ultrafast electron diffraction (UED) of cyclobutanone is predicted and analyzed. After excitation into the n-3s Rydberg state (S2), cyclobutanone can relax through two S2/S1 conical intersections, one characterized by compression of the CO bond and the other by dissociation of the α–CC bond. Subsequent transfer into the ground state (S0) is then achieved via two additional S1/S0 conical intersections that lead to three reaction pathways: α ring-opening, ethene/ketene production, and CO liberation. The isotropic gas-phase UED signal is predicted from the multistate MASH simulations, allowing for a direct comparison to the experimental data. This work, which is a contribution to the cyclobutanone prediction challenge, facilitates the identification of the main photoproducts in the UED signal and thereby emphasizes the importance of dynamics simulations for the interpretation of ultrafast experiments.

Chemistry↗
DOE OSTI2021

Experimental and computational investigation of the bond energy of thorium dicarbonyl cation and theoretical elucidation of its isomerization mechanism to the thermodynamically most stable isomer, thorium oxide ketenylidene cation, OTh + CCO

Collision-induced dissociation (CID) of [Th,2C,2O] + with Xe is performed using a guided ion beam tandem mass spectrometer (GIBMS). The only products observed are ThCO + and Th + by sequential loss of CO ligands. The experimental findings and theoretical calculations support that the structure of [Th,2C,2O] + is the bent homoleptic thorium dicarbonyl cation, Th + (CO) 2 , having quartet spin, which is both thermodynamically and kinetically stable enough in the gas phase to be observed in our GIBMS instrument. Analysis of the kinetic energy-dependent cross sections for this CID reaction yields the first experimental determination of the bond dissociation energy (BDE) of (CO)Th + –CO at 0 K as 1.05 ± 0.09 eV. A theoretical BDE calculated at the CCSD(T) level with cc-pVXZ (X = T and Q) basis sets and a complete basis set (CBS) extrapolation is in very good agreement with the experimental result. Although the doublet spin bent thorium oxide ketenylidene cation, OTh + CCO, is calculated to be the most thermodynamically stable structure, it is not observed in our experiment where [Th,2C,2O] + is formed by association of Th + and CO in a direct current discharge flow tube (DC/FT) ion source. Potential energy profiles of both quartet and doublet spin are constructed to elucidate the isomerization mechanism of Th + (CO) 2 to OTh + CCO. The failure to observe OTh + CCO is attributed to a barrier associated with C–C bond formation, which makes OTh + CCO kinetically inaccessible under our experimental conditions. Furthermore, chemical bonding patterns in low-lying states of linear and bent Th + (CO) 2 and OTh + CCO isomers are also investigated.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1985

Reversal ion source - A new source of negative ion beams

A new type of ion source utilizing beams of electrons and target molecules, rather than a diffuse, volume plasma, is described. The source utilizes an electrostatic electron 'mirror' which reverses trajectories in an electron beam, producing electrons at their turning point having a distribution of velocities centered at zero velocity. A gas which attaches zero-velocity electrons is introduced at this turning point. Negative ions are produced by an attachment or dissociative attachment process. For many of the thermal electron-attaching molecules the cross sections can be quite large, varying as the inverse square root of the electron energy or just the s-wave threshold law. The efficiency and current density of the ion source for production of Cl(-) through the large, thermal energy attachment process is estimated. It is argued that the source can be used for the production of negative ions through attachment resonances located at higher energies as well.

Orient, O. J.↗
NASA NTRS1991

Molecular line emission models of Herbig-Haro objects. I - H2 emission

A comprehensive model for molecular hydrogen emssion in Herbig-Haro objects that are associated with the heads of radiative stellar jets is presented by using a simple representation of the jet head as a comprising a leading bow shock and a trailing jet shock, separated by a dense layer of cool shocked gas. Attention is given to collisional excitation in a nondissociative shock and formation pumping in the molecular reformation zone behind a dissociative shock, employing detailed shock and photodissociation-region emission models that incorporate most of the relevant atomic physics and chemistry. The conditions under which each of these excitation mechanisms may be expected to contribute to the observed emission are discussed, and a general diagnostic scheme for discriminating among them is constructed. Applying this scheme to the HH 1-2 system, strong evidence for excitation by the radiation field of a fast shock is found. It is inferred that FUV pumping contributes a significant fraction of the H2 line emission, and it is shown that this can occur only if the UV pump lines are not strongly self-shielded.

Wolfire, Mark G.↗
NASA NTRS1992

An analysis of combustion studies in shock expansion tunnels and reflected shock tunnels

The effect of initial nonequilibrium dissociated air constituents on the combustion of hydrogen in high-speed flows for a simulated Mach 17 flight condition was investigated by analyzing the results of comparative combustion experiments performed in a reflected shock tunnel test gas and in a shock expansion tunnel test gas. The results were analyzed and interpreted with a one-dimensional quasi-three-stream combustor code that includes finite rate combustion chemistry. The results of this study indicate that the combustion process is kinetically controlled in the experiments in both tunnels and the presence of the nonequilibrium partially dissociated oxygen in the reflected shock tunnel enhances the combustion. Methods of compensating for the effect of dissociated oxygen are discussed.

Jachimowski, Casimir J.↗
NASA NTRS1991

Heterogeneous processes: Laboratory, field, and modeling studies

The efficiencies of chemical families such as ClO(x) and NO(x) for altering the total abundance and distribution of stratospheric ozone are controlled by a partitioning between reactive (active) and nonreactive (reservoir) compounds within each family. Gas phase thermodynamics, photochemistry, and kinetics would dictate, for example, that only about 1 percent of the chlorine resident in the lower stratosphere would be in the form of active Cl or ClO, the remainder existing in the reservoir compounds HCl and ClONO2. The consistency of this picture was recently challenged by the recognition that important chemical transformations take place on polar regions: the Airborne Antarctic Ozone Experiment (AAOE) and the Airborne Arctic Stratospheric Expedition (AASA). Following the discovery of the Antarctic ozone hole, Solomon et al. suggested that the heterogeneous chemical reaction: ClONO2(g)+HCl(s) yields Cl2(g)+HNO3(s) could play a key role in converting chlorine from inactive forms into a species (Cl2) that would rapidly dissociate in sunlight to liberate atomic chlorine and initiate ozone depletion. The symbols (s) and (g) denote solid phase, or adsorbed onto a solid surface, and gas phase, respectively, and represent the approach by which such a reaction is modeled rather than the microscopic details of the reaction. The reaction was expected to be most important at altitudes where PSC's were most prevalent (10 to 25 km), thereby extending the altitude range over which chlorine compounds can efficiently destroy ozone from the 35 to 45 km region (where concentrations of active chlorine are usually highest) to lower altitudes where the ozone concentration is at its peak. This chapter will briefly review the current state of knowledge of heterogeneous processes in the stratosphere, emphasizing those results obtained since the World Meteorological Organization (WMO) conference. Sections are included on laboratory investigations of heterogeneous reactions, the characteristics and climatology of PSC's, stratospheric sulfate aerosols, and evidence of heterogeneous chemical processing.

Poole, Lamont R.↗
DOE OSTI2024

Association Kinetics for Perfluorinated n -Alkyl Radicals

Radical-radical reaction channels are important in the pyrolysis and oxidation chemistry of perfluoroalkyl substances (PFAS). In particular, unimolecular dissociation reactions within unbranched n-perfluoroalkyl chains, and their corresponding reverse barrierless association reactions, are expected to be significant contributors to the gas-phase thermal decomposition of families of species such as perfluorinated carboxylic acids and perfluorinated sulfonic acids. Unfortunately, experimental data for these reactions are scarce and uncertain. Furthermore, obtaining reliable theoretical predictions for such reactions is a laborious and computationally intensive task. Here, in this work, the chemical kinetics of the various association/decomposition reactions producing/decomposing the C 2 -C 4 series of unbranched n-perfluoroalkanes (C 2 F 6 , C 3 F 8 , and C 4 F 10 ) are examined using state-of-the-art ab initio transition-state-theory-based master-equation calculations. The variable-reaction-coordinate transition-state theory (VRC-TST) formalism is employed in computing the microcanonical and canonical rates for the association reactions. Reaction thermochemistry is obtained via composite quantum chemistry calculations and the laddering of error-canceling reaction schemes via a connectivity-based hierarchy approach employing ANL1/ANL0-style reference energies. Lennard-Jones collision model parameters for the considered systems were estimated by a direct dynamics approach, and collisional energy transfer parameters were obtained from analogies to systems of similar size and heavy-atom connectivity. A one-dimensional master equation approach was used to convert the microcanonical rate coefficients from the VRC-TST analysis into temperature- and pressure-dependent rate constants for the association reactions and the reverse dissociation reactions. The data are reported in standardized formats for usage in comprehensive chemical kinetic models for PFAS thermal destruction.

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

Photo-excitation of long-lived transient intermediates in ultracold reactions

In many chemical reactions, the transformation from reactants to products is mediated by transient intermediate complexes. For gas-phase reactions involving molecules with a few atoms, these complexes typically live on the order of 10 ps or less before dissociating, and are therefore rarely influenced by external processes. Here, we demonstrate that the transient intermediate complex K 2 Rb 2 *, formed from collisions between ultracold KRb molecules, undergoes rapid photo-excitation in the presence of a continuous-wave laser source at 1,064 nm, a wavelength commonly used to confine ultracold molecules. These excitations are facilitated by the exceptionally long lifetime of the complex under ultracold conditions. Indeed, by monitoring the change in the complex population after the sudden removal of the excitation light, we directly measure the lifetime of the complex to be 360 ± 30 ns, in agreement with our calculations based on the Rice–Ramsperger–Kassel–Marcus (RRKM) statistical theory. Furthermore, our results shed light on the origin of the two-body loss widely observed in ultracold molecule experiments. Additionally, the long complex lifetime, coupled with the observed photo-excitation pathway, opens up the possibility to spectroscopically probe the structure of the complex with high resolution, thus elucidating the reaction dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Comet Shoemaker-Levy-9 impact with Jupiter: Aeronomical predictions

The fragments of comet Shoemaker-Levy-9 will enter the atmosphere of Jupiter during July 20-26, 1994. Significant amounts of water vapor will be injected into the upper atmosphere of Jupiter either from the comet itself or from the lower atmosphere of Jupiter. The photochemistry of both the neutral gas and the ionosphere will be greatly altered by the influx of this water vapor or the atomic oxygen generated by the dissociation of the water. Enhanced abundances of H2O (or other species such as NH3) in the atmosphere above the homopause should persist for at least a year and should be globally distributed. The odd oxygen (i.e., O or H2O or OH) associated with the cometary water influx alters the ion chemistry by removing H(+) ions, which also has the effect of reducing the ionospheric electron density because H(+) is ordinarily the main ion species in the Jovian ionosphere. The density of H3(+), both in the auroral and non-auroral ionosphere, will also be reduced due to presence of water. This ion species has been detected spectroscopically at Jupiter, and a drop in its abundance should be detectable. The major ion species will become H3O(+) which could reach a peak density as high as 10(exp 4)/cu cm in the non-auroral ionosphere and 10(exp 5)/cu cm in the auroral ionosphere. It should be possible to detect this ion species spectroscopically from Earth-based observatories.

Cravens, T. E.↗