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Results for “dissociation reaction”

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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
NASA NTRS1977

Product distributions for some thermal energy charge transfer reactions of rare gas ions

Ion cyclotron resonance methods were used to measure the product distributions for thermal-energy charge-transfer reactions of He(+), Ne(+), and Ar(+) ions with N2, O2, CO, NO, CO2, and N2O. Except for the He(+)-N2 reaction, no molecular ions were formed by thermal-energy charge transfer from He(+) and Ne(+) with these target molecules. The propensity for dissociative ionization channels in these highly exothermic charge-transfer reactions at thermal energies contrasts with the propensity for formation of parent molecular ions observed in photoionization experiments and in high-energy charge-transfer processes. This difference is explained in terms of more stringent requirements for energy resonance and favorable Franck-Condon factors at thermal ion velocities.

Anicich, V. G.↗
DOE OSTI2021

Parabolic oxidation kinetics of a plutonium alloy at room temperature

Auger electron spectroscopy (AES) was used to characterize the oxide scale formed on an ~0.5 wt. % Ga plutonium metal alloy. Analysis of changes to the characteristic Auger transitions for Pu and O during sputter depth profiles were used in combination with previously measured sputter yields to determine the thickness of the oxide scale and provide insight into its chemistry. From this data, the parabolic kinetics for the Pu-Ga alloy were determined as a function of relative humidity, RH = 14–92%, and oxygen partial pressure, p(O 2 ) = 31–157 Torr, at 25°C. For each relative humidity investigated, the parabolic rate constant was found to be independent of oxygen partial pressure. Furthermore, power-law fits to the relative humidity effect on the rate constant was found to have a power of n = 1.265, indicating the diffusion species which rate-limits the reaction isn’t molecular water, which subsequent dissociates at the oxide-metal interface, or hydroxyl from dissociation at the gas-surface interface.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Quantifying the Decomposition Kinetics of Linear C 2 –C 4 Perfluoroalkanes

The pyrolysis of C 2 –C 4 linear perfluoroalkanes was investigated using laser schlieren densitometry (LS) in a diaphragmless shock tube. Mixtures of 1, 2, and 4% perfluoroethane (PFE), perfluoropropane (PFP), and perfluorobutane (PFB) in excess krypton were shock-heated to 1400–2500 K at pressures of 60, 120, and 240 Torr. The initiation step for all perfluoroalkanes involved carbon–carbon bond fission. The rate constants for unimolecular decomposition were computed using microcanonical rate theory, and these rate constants were combined into a detailed chemical kinetic mechanism. For PFE and PFP, there was one dissociation channel, while PFB dissociated via two competing bond-fission reactions. The perfluoroalkyl radicals subsequently recombined or underwent further unimolecular decomposition. In conclusion, the kinetic model accurately simulated the density gradient profiles of all perfluoroalkanes.

Guzman, Eduardo H. [Brown Univ., Providence, RI (U↗
DOE OSTI2025

Density Functional Tight-Binding Enables Tractable Studies of Quantum Plasmonics

Routine investigations of plasmonic phenomena at the quantum level present a formidable computational challenge due to the large system sizes and ultrafast time scales involved. This Feature Article highlights the use of density functional tight-binding (DFTB), particularly its real-time time-dependent formulation (RT-TDDFTB), as a tractable approach to study plasmonic nanostructures from a quantum mechanical purview. We begin by outlining the theoretical framework and limitations of DFTB, emphasizing its efficiency in modeling systems with thousands of atoms over picosecond time scales. Applications of RT-TDDFTB are then explored in the context of optical absorption, nonlinear harmonic generation, and plasmon-mediated photocatalysis. We demonstrate how DFTB can reconcile classical and quantum descriptions of plasmonic behavior, capturing key phenomena such as size-dependent plasmon shifts and plasmon coupling in nanoparticle assemblies. Lastly, we showcase DFTB’s ability to model hot carrier generation and reaction dynamics in plasmon-driven H2 dissociation, underscoring its potential to model photocatalytic processes. Collectively, these studies establish DFTB as a powerful, yet computationally efficient tool to probe the emergent physics of materials at the limits of space and time.

Electrical energy↗
DOE OSTI2025

Electrochemical Corrosion and Catalysis Dynamics of Tin Oxide during Water Oxidation

Metal oxide corrosion severely limits anodic electrocatalysis, particularly at high potentials in acidic environments, where degradation pathways remain poorly defined. This study establishes explicit connections between corrosion and electrocatalysis on tin oxide during water oxidation by examining the roles of lattice defects, reactive oxygen species, interfacial pH variations, and speciation of corroded tin in acid. We first demonstrate the presence of structural defects such as oxygen vacancies and substoichiometric Sn(II) species by integrating electron paramagnetic resonance spectroscopy, ultraviolet photoelectron spectroscopy, and Mott–Schottky analysis. Kohn–Sham density functional theory calculations reveal that explicit water structures thermodynamically stabilize reaction intermediates and lower reaction overpotentials. Moreover, we propose that water dissociation leads to hydrogen-bonding networks formed by H* and OH* intermediates, which may span the entire catalyst surface and decrease the interfacial pH to drive corrosion. In contrast, the electrochemical generation of reactive oxygen species is shown to play a minor role in catalyst corrosion during water oxidation using inductively coupled plasma mass spectrometry coupled with selective chemical scavengers. Square-wave voltammetry combined with rotating ring-disk electrodes is used to reveal that under open-circuit conditions, only Sn(IV) cations chemically dissolve from tin oxide, while both Sn(IV) and Sn(II) species electrochemically corrode during water oxidation. Our results unveil a dynamic and complicated interplay between corrosive and catalytic pathways on metal oxide electrocatalysts: a decrease in interfacial pH due to water oxidation exacerbates Sn(II)/Sn(IV) corrosion. Subsequently, the electrochemical corrosion of Sn(II)/Sn(IV) facilitates product formation from lattice oxygen, while the redeposition of corroded Sn(II) as Sn(IV) can enable oxygen exchange with water. By elucidating the roles of defects and interfacial chemistry, this work provides a roadmap for engineering improved electrocatalysts that balance activity and stability, a critical step toward scalable and durable energy technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Mechanism of Methanol Decomposition over Single-Site Pt 1 /CeO 2 Catalyst: A DRIFTS Study

Single-site catalysts have drawn broad attention in catalysis because of their maximum atomic utilization and unique catalytic performance. Early work in our group has shown a 40-fold higher activity of methanol decomposition over single-site Pt 1 /CeO 2 catalyst than CeO 2 supported 2.5 nm Pt nanoparticles, while a molecular-level understanding of such enhancement is lacking. Herein, the reaction mechanism of methanol decomposition over Pt 1 /CeO 2 was carefully investigated using in situ DRIFTS, and a reaction pathway was proposed. Methanol molecules were dissociatively adsorbed on nanoceria support first, followed by the diffusion of as-formed methoxy species onto Pt single sites where the dehydrogenation occurs and results in the weakly bonded CO. The ease of methanol dissociative adsorption on nanoceria support and the tailored electronic property of Pt 1 via the metal-support interaction are believed to be strongly correlated with the high activity of Pt 1 /CeO 2 .

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

Time-resolved relaxation and fragmentation of polycyclic aromatic hydrocarbons investigated in the ultrafast $\mathrm{XUV}$-$\mathrm{IR}$ regime

Polycyclic aromatic hydrocarbons (PAHs) play an important role in interstellar chemistry and are subject to high energy photons that can induce excitation, ionization, and fragmentation. Previous studies have demonstrated electronic relaxation of parent PAH monocations over 10–100 femtoseconds as a result of beyond-Born-Oppenheimer coupling between the electronic and nuclear dynamics. Here, we investigate three PAH molecules: fluorene, phenanthrene, and pyrene, using ultrafast XUV and IR laser pulses. Simultaneous measurements of the ion yields, ion momenta, and electron momenta as a function of laser pulse delay allow a detailed insight into the various molecular processes. We report relaxation times for the electronically excited PAH * , PAH +* and PAH 2+* states, and show the time-dependent conversion between fragmentation pathways. Additionally, using recoil-frame covariance analysis between ion images, we demonstrate that the dissociation of the PAH 2+ ions favors reaction pathways involving two-body breakup and/or loss of neutral fragments totaling an even number of carbon atoms.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Revealing the Reaction Path of UVC Bond Rupture in Cyclic Disulfides with Ultrafast X-ray Scattering

Disulfide bonds are ubiquitous molecular motifs that influence the tertiary structure and biological functions of many proteins. Yet it is well known that the disulfide bond is photolabile when exposed to UVC radiation. The deep-UV induced S-S bond fragmentation kinetics on very fast time scales are especially pivotal to fully understand the photostability and photodamage repair mechanisms in proteins. In 1,2-dithiane, the smallest saturated cyclic molecule that mimics biologically active species with S-S bonds, we investigate the photochemistry upon 200 nm excitation by femtosecond time-resolved X-ray scattering in the gas phase using an X-ray free electron laser. In the femtosecond time domain, we discover a very fast reaction that generates molecular fragments with one and two sulfur atoms. On picosecond and nanosecond timescales, a complex network of reactions unfolds that, ultimately, completes the sulfur dissociation from the parent molecule.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Developing a low-cost renewable supply of hydrogen with high-temperature electrochemistry

Abstract Producing inexpensive hydrogen using electricity to split water or to extract hydrogen from hydrocarbon compounds is a two-sided coin: one side is obtaining and exploiting low-cost, emissions-free energy sources while the opposite side is establishing low-cost robust, durable, and efficient materials for the conversion processes. This article explores the materials needed for water splitting electrolysis, electrochemical abstraction of hydrogen from light alkanes, and looping thermal-chemical reaction processes that typically form and then dissociate an acid compound in a two- or three-step process. The focus is on the R&D needs of materials that are used for high-temperature electrochemistry, focusing on solid-oxide, ion-conducting cell materials sets (SOECs). To exploit the availability of low-cost electricity, these materials must stand up to cyclic operations. They also must be durable for years of service to reduce operating and maintenance costs, and they must achieve high conversion efficiencies to avoid large, energy-intensive recycle loops. Graphical abstract

Boardman, Richard D.↗
NASA NTRS1972

Measurements of the structure of an ionizing shock wave in a hydrogen-helium mixture

Shock structure during ionization of a hydrogen-helium mixture was studied using hydrogen line and continuum emission measurements. A reaction scheme is proposed which includes hydrogen dissociation and a two-step excitation-ionization mechanism for hydrogen ionization by atom-atom and atom-electron collisions. Agreement was achieved between numerical calculations and measurements of emission intensity as a function of time for shock velocities from 13 to 20 km/sec in a 0.208 H2 - 0.792 He mixture. The electron temperature was found to be significantly different from the heavy particle temperature during much of the ionization process. Similar time histories for H beta and continuum emission indicate upper level populations of hydrogen in equilibrium with the electron concentration during the relaxation process.

Leibowitz, L. P.↗
NASA NTRS1973

Measurements of the structure of an ionizing shock wave in a hydrogen-helium mixture.

Shock structure during ionization of a hydrogen-helium mixture has been followed using hydrogen line and continuum emission measurements. A reaction scheme is proposed which includes hydrogen dissociation and a two-step excitation-ionization mechanism for hydrogen ionization by atom-atom and atom-electron collisions. Agreement has been achieved between numerical calculations and measurements of emission intensity as a function of time for shock velocities from 13 to 20 km/sec in a 0.208 H2-0.792 He mixture. The electron temperature was found to be significantly different from the heavy particle temperature during much of the ionization process. Similar time histories for H beta and continuum emission indicate upper level populations of hydrogen in equilibrium with the electron concentration during the relaxation process.

Leibowitz, L. P.↗
NASA NTRS1980

Direct thermal water splitting by concentrated solar radiation for hydrogen production. Phase O: Proof of concept experiment

The direct production of hydrogen from water and solar energy concentrated into a high temperature aperture is described. A solar powered reactor able to dissociate water vapor and to separate the reaction product at high temperature was developed, and direct water splitting has been achieved in a laboratory reactor. Water vapor and radiative heating from a carbon dioxide laser are fed into the reactor, and water vapor enriched in hydrogen and water vapor enriched in oxygen are produced. The enriched water vapors are separated through a separation membrane, a small disc of zirconium dioxide heated to a range of 1800 k to 2800 k. To avoid water vapor condensation within the reactor, the total pressure within the reactor was limited to 0.15 torr. A few modifications would enable the reactor to be operated at an increased pressure of a few torrs. More substantial modifications would allow for a reaction pressure of 0.1 atmosphere.

Genequand, P.↗
NASA NTRS1986

Electromagnetic dissociation effects in galactic heavy-ion fragmentation

Methods for calculating cross sections for the breakup of galactic heavy ions by the Coulomb fields of the interacting nuclei are presented. By using the Weizsacker-Williams method of virtual quanta, estimates of electromagnetic dissociation cross sections for a variety of reactions applicable to galactic cosmic ray shielding studies are presented and compared with other predictions and with available experimental data.

Norbury, J. W.↗
NASA NTRS1987

Computational chemistry

With the advent of supercomputers, modern computational chemistry algorithms and codes, a powerful tool was created to help fill NASA's continuing need for information on the properties of matter in hostile or unusual environments. Computational resources provided under the National Aerodynamics Simulator (NAS) program were a cornerstone for recent advancements in this field. Properties of gases, materials, and their interactions can be determined from solutions of the governing equations. In the case of gases, for example, radiative transition probabilites per particle, bond-dissociation energies, and rates of simple chemical reactions can be determined computationally as reliably as from experiment. The data are proving to be quite valuable in providing inputs to real-gas flow simulation codes used to compute aerothermodynamic loads on NASA's aeroassist orbital transfer vehicles and a host of problems related to the National Aerospace Plane Program. Although more approximate, similar solutions can be obtained for ensembles of atoms simulating small particles of materials with and without the presence of gases. Computational chemistry has application in studying catalysis, properties of polymers, all of interest to various NASA missions, including those previously mentioned. In addition to discussing these applications of computational chemistry within NASA, the governing equations and the need for supercomputers for their solution is outlined.

Arnold, J. O.↗
NASA NTRS2006

Electron-Impact Ionization and Dissociative Ionization of Biomolecules

It is well recognized that secondary electrons play an important role in radiation damage to humans. Particularly important is the damage of DNA by electrons, potentially leading to mutagenesis. Molecular-level study of electron interaction with DNA provides information on the damage pathways and dominant mechanisms. Our study of electron-impact ionization of DNA fragments uses the improved binary-encounter dipole model and covers DNA bases, sugar phosphate backbone, and nucleotides. An additivity principle is observed. For example, the sum of the ionization cross sections of the separate deoxyribose and phosphate fragments is in close agreement with the C3(sup prime)- and C5 (sup prime)-deoxyribose-phospate cross sections, differing by less than 5%. Investigation of tandem double lesion initiated by electron-impact dissociative ionization of guanine, followed by proton reaction with the cytosine in the Watson-Crick pair, is currently being studied to see if tandem double lesion can be initiated by electron impact. Up to now only OH-induced tandem double lesion has been studied.

Huo, Winifred M.↗
NASA NTRS2017

Deep K-Band Observations of TMC-1 with the Green Bank Telescope: Detection of HC7O, Nondetection of HC11N, and a Search for New Organic Molecules

The 100 m Robert C. Byrd Green Bank Telescope K-band (KFPA) receiver was used to perform a high-sensitivity search for rotational emission lines from complex organic molecules in the cold interstellar medium toward TMC-1 (cyanopolyyne peak), focussing on the identification of new carbon-chain-bearing species as well as molecules of possible prebiotic relevance. We report a detection of the carbon-chain oxide species HC7O and derive a column density of (7.8 ± 0.9) ´ 10(exp 11) per sq. cm. This species is theorized to form as a result of associative electron detachment reactions between oxygen atoms and C7H(−), and/or reaction of C6H2(+) with CO (followed by dissociative electron recombination). Upper limits are given for the related HC6O, C6O, and C7O molecules. In addition, we obtained the first detections of emission from individual 13C isotopologues of HC7N, and derive abundance ratios HC7N/HCCC13CCCCN = 110 ± 16 and HC7N/HCCCC13CCCN = 96 ± 11, indicative of significant 13C depletion in this species relative to the local interstellar elemental 12C/13C ratio of 60–70. The observed spectral region covered two transitions of HC11N, but emission from this species was not detected, and the corresponding column density upper limit is 7.4 x 10(exp 10) per sq. cm (at 95% confidence). This is significantly lower than the value of 2.8 x 10(exp 11) per sq. cm previously claimed by Bell et al. and confirms the recent nondetection of HC11N in TMC-1 by Loomis et al. Upper limits were also obtained for the column densities of malononitrile and the nitrogen heterocycles quinoline, isoquinoline, and pyrimidine.

ISM: abundances – ISM: lines and bands – ISM: mole↗
DOE OSTI2021

Plasma-assisted catalysis for ammonia synthesis in a dielectric barrier discharge reactor: key surface reaction steps and potential causes of low energy yield

Ammonia synthesis experiments were carried out in a coaxial dielectric barrier discharge (DBD) reactor packed with several different supports and metal catalysts. There was a marked increase in the reaction rate, over that obtained in an empty DBD plasma reactor, upon introduction of a packed bed of γ-Al 2 O 3 , Ru/γ-Al 2 O 3 , or SiO 2 particles. The difference in the reaction rates over γ-Al 2 O 3 and Ru/γ-Al 2 O 3 was minimal. Complementary zero-dimensional plasma kinetic model analysis was also performed using inputs from experimental data. This kinetic analysis allowed for gas phase reactions, Eley–Rideal (E–R) reactions, and direct adsorption of radical species on the γ-Al 2 O 3 surface. On the metal surface, dissociative adsorption of N 2 and H 2 , and Langmuir–Hinshelwood reactions were also included. This analysis revealed that, under the conditions of our experiments, ammonia synthesis proceeds principally by the formation of reactive radicals in the gas phase, which then adsorb and participate in E–R reactions on both the metal and support material surfaces. Furthermore, this finding illustrates a challenge for substantially increasing the energy yield for plasma-assisted ammonia synthesis in typical DBD reactors containing packed catalyst beads.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗