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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Universal crossed beam imaging studies of polyatomic reaction dynamics

The marriage between high level quantum calculations and experimental advances in laser technology, quantum state control, and detection techniques have opened the door to the study of molecular collision dynamics at a new level of detail. However, one current challenge lies in adapting these powerful strategies to address questions beyond the scope of the small ground state systems that have largely been the focus of reaction dynamics investigations to-date. For molecules with intermediate or large size (more than 6 atoms), lack of spectroscopic information and spectral congestion limit quantum state preparation, control and detection for experiment, and the large number of degrees of freedom of the system makes accurate quantum dynamics calculations prohibitively expensive. Nevertheless, studies of the chemical dynamics of such systems can reveal novel aspects of reactivity not anticipated based upon the behavior of smaller model systems. This Perspective will highlight applications of soft vacuum ultraviolet photoionization at 157 nm as a universal probe in combination with crossed beams and DC slice velocity map ion imaging to study bimolecular reaction dynamics of molecules of intermediate or large size, illuminated with support of high-level ab initio calculations. In this work, we report on the chemical dynamics of atomic oxygen or chlorine reactions with organic compounds: propanol isomers, alkylamines (N(CH 3 ) 3 and NH(CH 3 ) 2 ), and isobutene ((CH 3 ) 2 CCH 2 ) studied using this approach. The polyatomic radical products from the hydrogen abstraction process have been detected by 157 nm photoionization and their slice ion images embody translational energy and angular information that directly reflect the underlying collision dynamics. Various reaction mechanisms (such as direct abstraction and addition–elimination) along with the involvement of roaming dynamics and novel intersystem crossing pathways are presented. These demonstrate the power of this technique to reveal fundamentally new aspects of reaction dynamics that arise in larger reaction systems.

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

From cellulose to 1,2,4-benzenetriol via catalytic degradation over a wood-based activated carbon catalyst

In this study, spherical P-doped activated carbon (CSP) was obtained from poplar bark by microwave carbonization with phosphoric acid as the dopant and activating agent. Phosphorus bonded with four oxygen atoms to form a phosphate-like structure rather than directly bonding with C atoms in CSP; such groups can provide Lewis acid active sites with moderately strong acidity. The Lewis acid and total acid content increased with increasing phosphoric acid doping ratio. The use of phosphoric acid as an activating agent promotes the formation of a developed porous structure. CSP 1 (mass ratio of raw material to acid = 1 : 1) had a specific surface area of 1115 m 2 g –1 with developed micro–mesoporous structures, mainly micropores. Investigation of the activity of CSP in catalytic cellulose hydrolysis during hydrothermal degradation showed that Brønsted acid sites promote hydrolysis and dehydration of cellulose, Lewis acid sites promote subsequent reactions such as isomerization, rearrangement, and oligomerization, and the developed pores can provide reaction sites and facilitate reactant transportation. The optimal reaction conditions, i.e. , 1 h at 230 °C and 1 MPa with CSP 1 (0.4 g) as the catalyst, gave a cellulose conversion of >99.9%, with 42.30% selectivity for 1,2,4-benzenetriol. This study provides an effective method for preparing 1,2,4-benzenetriol from cellulose with biomass-based activated carbon as the catalyst, which enables green synthesis of 1,2,4-benzenetriol and promotes the use of biomass waste resources.

1,2,4-benzenetriol↗
DOE OSTI2021

Theoretical and experimental study on the O( 3 P) + 2,5-dimethylfuran reaction in the gas phase

In this work we report a joint experimental and computational study on the 2,5-dimethylfuran oxidation reaction in the gas phase initiated by atomic oxygen O( 3 P). The experiments have been performed by using vacuum-ultraviolet synchrotron radiation at the Advanced Light Source (ALS) of the Lawrence Berkeley National Laboratory (LBNL), at a temperature of 550 K and a pressure of 8 Torr. The experimental data were supported by quantum-chemical calculations along with a kinetic model, also taking into account the possible involvement of different magnetic states, performed in the framework of the RRKM theory. Propyne, acetaldehyde, methylglyoxal, dimethylglyoxal, 3-penten-2-one, 2,5-dimethylfuran-3(2 H )-one, and 1,2-diacetyl ethylene have been identified as the main primary products arising under the conditions of the experiment. Our computational model suggests that these species can be formed at the concentration and branching ratio experimentally observed only in the presence of a non-negligible fraction of non-thermalized intermediates.

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

Atomic autoionization in the photo-dissociation of super-excited deuterated water molecules fragmenting into D + + O + + D

We present the relaxation dynamics of deuterated water molecules via autoionization, initiated by the absorption of a 61 eV photon, producing the very rare D + + O + + D breakup channel. We employ the COLd target recoil ion momentum spectroscopy method to measure the 3D momenta of the ionic fragments and emitted electrons from the dissociating molecule in coincidence. We interpret the results using the potential energy surfaces extracted from multi-reference configuration interaction calculations. The measured particle energy distributions can be related to a super-excited monocationic state located above the double ionization threshold of D 2 O. The autoionized electron energy shows a sharp distribution centered around 0.5 eV, which is a signature of the atomic oxygen autoionization occurring in the direct and sequential dissociation processes of D 2 O + * at a large internuclear distance. In this way, an O + radical fragment and a low-energy electron are created, both of which can trigger secondary reactions in their environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Synthesis and characterization of 5,15-bis(hydroxymethyl)porphyrins – simple compounds distantly inspired by the chlorosomal bacteriochlorophylls

A self-assembly paradigm is provided in green photosynthetic bacteria by the chlorin macrocycle bacteriochlorophyll (BChl) c, which contains a 3-(1-hydroxyethyl) substituent, central magnesium ion, and 13-keto group. The assembled BChl c structure is a powerful light-harvesting apparatus that can support life even under extreme low-light conditions. Here, inspired by the work of Balaban, two far simpler porphyrins have been synthesized, 5,15-bis(hydroxymethyl)-10,20-diphenylporphinatozinc(II) (Ph/CH 2 OH) and 5,15-bis(hydroxymethyl)porphinatozinc(II) (H/CH 2 OH), and analogues wherein ethyl replaces hydroxymethyl (Ph/Et and H/Et). Examination of Ph/CH 2 OH and H/CH 2 OH by time-resolved spectroscopy showed an ∼2-fold enhancement in the singlet excited-state lifetime compared to meso-tetraphenylporphinatozinc(II) (ZnTPP). The single-crystal X-ray diffraction revealed distinct packing patterns. Porphyrin Ph/CH 2 OH exhibited double staircases wherein (1) each zinc is pentacoordinate (by apical coordination of one hydroxymethyl group of a porphyrin in the same staircase), (2) the second hydroxymethyl group is hydrogen-bonded to an apically coordinated hydroxymethyl oxygen atom in the adjacent staircase, (3) the porphyrins in a given staircase are coplanar but cofacially offset with each other, and (4) the adjacent staircases are oriented approximately 72° relative to each other. Porphyrin H/CH 2 OH assembled wherein (1) each zinc is hexacoordinate by ligation of hydroxymethyl moieties, (2) each hydroxymethyl –OH is hydrogen-bonded with an acetonitrile solvent molecule in the lattice, and (3) the planes of the four nearest neighbor porphyrins are essentially perpendicular to a given porphyrin. Study of the solid-state packing patterns of sparsely substituted porphyrins enables insights into how the structural design of tetrapyrroles can guide their aggregate self-assembly.

Tran, Vy-Phuong [North Carolina State University, ↗
DOE OSTI2025

Mechanistic study of a CO-free pathway in the methanol oxidation reaction over oxygen vacancies in NiOOH

The methanol oxidation reaction is a key reaction in direct methanol fuel cells. Prior research indicates that if oxygen vacancies in NiOOH serve as the active sites, the methanol oxidation mainly proceeds through the formate-involving pathway, which is a CO-free pathway, distinct from the conventional path over transition metal catalysts, though the fundamental reason for this suppressed CO formation is unclear. Herein, we report density functional theory calculations, through which we uncover the underlying reasons for this alternate path of methanol oxidation over the oxygen vacancies in NiOOH. We find that the existence of oxygen vacancies in NiOOH affects the adsorption configuration of adsorbates and that the interfacial charge transfer is minimal for CHO and CO intermediates. In addition, CHO, a key intermediate to form CO, adsorbs at the oxygen vacancy through the oxygen atom, leading to low stability due to the incomplete valence saturation of the carbon atom. This weak electronic interaction and instability effectively inhibit CHO formation and, consequently, CO formation. These insights provide valuable guidance for the development of efficient and CO-tolerant catalysts for methanol oxidation.

Ho, Thy [University of Oklahoma, Norman, OK (Unite↗
DOE OSTI2026

Chemical and morphological evolution of hybrid conversion coatings in low-Earth orbit space environment

Understanding how protective coatings respond to the harsh low-Earth orbit (LEO) environment is essential for ensuring the safety, longevity, and cost-effectiveness of spacecraft. In particular, identifying environmentally friendly, non-chromate alternatives that can maintain performance under such conditions has both technological and regulatory significance. This study investigates the environmental stability of zirconium-based hybrid conversion coatings with Cu additives (Cu10 and Cu20) applied to cold-rolled steel, tested in the Materials International Space Station Experiment (MISSE) outside the International Space Station (ISS). Chemical and morphological analyses were carried out using a combination of electron microscopy and X-ray spectroscopy techniques, including scanning electron microscopy (SEM), scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy (STEM-EDS), X-ray photoelectron spectroscopy (XPS), and X-ray absorption near-edge structure (XANES) spectroscopy. After exposure outside the ISS, all coatings remained structurally intact, with all exhibiting a uniform Zr-rich matrix and embedded Cu-rich clusters, while a thin Si-rich surface layer developed from interaction with space environments. Depth-resolved XPS showed a layered structure with CuO on the surface, Cu 2 O, and partial Zr(IV) reduction near Cu-rich sites, evidence of Atomic Oxygen (AO)-driven surface oxidation. These results demonstrate that Cu–Zr coatings maintain their chemical integrity and microstructure in harsh space environments, offering a non-chromate alternative for long-term aerospace protection. These insights provide valuable guidance for developing next-generation protective coatings that combine environmental sustainability with the reliability required for future aerospace and orbital applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Morphology and reactivity of size-selected titanium oxide nanoclusters on Au(111)

The morphology and reactivity of mass-selected titania clusters, Ti 3 O 6 and Ti 3 O 5 , deposited onto Au(111) were studied by scanning tunneling microscopy (STM) and temperature programmed desorption (TPD). Despite differing by only one oxygen atom, the stoichiometric Ti 3 O 6 and the sub-stoichiometric (“reduced”) Ti 3 O 5 clusters exhibit very different structures and preferred binding sites. The Ti 3 O 6 clusters preferentially bind at step edges and form small assemblies (2-4 clusters) on Au terraces, while the “reduced” Ti 3 O 5 clusters form much larger fractal-like assemblies that can extend across step boundaries. Annealing the Ti 3 O 5,6 /Au(111) systems to higher temperatures causes changes in the size-distributions of cluster assemblies but does not lead to the formation of TiO x nanoislands for temperatures ≤ 700 K. Reactivity studies show that the reduced Ti 3 O 5 cluster has higher activity than Ti 3 O 6 for 2-propanol dehydration, although both clusters exhibit substantial activity for dehydrogenation to acetone. Calculations using DFT+U suggest that the differences in aggregate morphology and reactivity are associated with the number of undercoordinated Ti 3c sites in the supported clusters.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Laser transport and backscatter in low-density SiO 2 and Ta2O 5 foams

Experiments using a single 527 nm wavelength beam interacting with sub- and supercritical density SiO 2 and Ta 2 O 5 foams examined laser propagation and backscatter from laser–plasma instabilities such as Stimulated Brillouin Scattering (SBS). Two densities of each material were examined, and multiple diagnostics were used to characterize the propagation and backscatter. For 5 mg/cc SiO 2 (n e /n c = 0.375), the laser propagation distance was well approximated by treating the foam as a gas. However, for the 2 mg/cc SiO 2 foam (n e /n c = 0.15), the same model over-predicts the propagation distance by ~40%. Furthermore, existing analytical theories on propagation through subcritical foams were able to account for this difference. The laser heat wave propagated ~1/2 as far in Ta 2 O 5 than SiO 2 foams with similar electron density. We showed that this difference is due to the increased radiation losses in the higher Z foam. The fraction of backscattered light scales linearly with incident laser intensity for the range of intensities examined. Ta 2 O 5 foams had significantly lower levels of backscatter (1–3%) than the SiO 2 (4–8%), which is consistent with estimates of large Landau damping due to the presence of the oxygen atoms. The measured fraction of SBS backscattered laser energy for a 2 mg/cc SiO 2 foam shot was ~4 times lower than predicted by simulations assuming a gas-like foam. We found that we needed to assume increased ion heating such that T i /T e ~1.2–1.5 in the plasma to agree with the measured SBS reflectivity. Analytical models of laser-heated foams predict preferential heating of the ions as has been observed in previous experiments.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Laser absorption measurements of electron density in nanosecond-scale atmospheric pressure pulsed plasmas

We report on time-resolved measurements of electron number density by continuous-wave laser absorption in a low-energy nanosecond-scale laser-produced spark in atmospheric pressure air. Laser absorption is a result of free-free and bound-free electron excitation, with the absorption coefficient modeled and evaluated using estimates of the time-variation in electron temperature and probe laser absorption path length. Plasma electron number densities are determined to be as high as n e = 7 x 10 19 cm -3 , and decay to 1/e of their peak values over a period of about 50 ns following plasma formation using a 20 mJ, 10 ns pulse width frequency-doubled Nd:YAG laser. The measured plasma densities at later times are shown to be in reasonable agreement with Stark broadening measurements of the 3s[ 5 S o ]-3p[ 5 P] electronic transition in atomic oxygen at 777 nm. This study provides support for the use of such continuous wave laser absorption for time resolved electron density measurements in low energy spark discharges in air, provided that an estimate of the electron temperature and laser path length can be made by accompanying diagnostics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Spectrally filtered ps–ns emission dynamics of atmospheric-pressure nanosecond pulsed plasmas

The temporal dynamics of atmospheric-pressure nanosecond pulsed plasma discharges in a pin-to-pin electrode configuration are studied using streak-camera line imaging of the interelectrode gap with a time resolution as short as ~25 ps. Discharge emission initiates homogeneously throughout the interelectrode gap with no detectable streamer propagation and then temporally decays in two distinct phases. Plasma emission bands attributed to various electronic transitions are tracked for single discharges in air and N 2 . Spectral filtering of the excited molecular states reveals that the N 2 (C–B) and N 2 (B–A) emission bands evolve in distinct early and late phases, respectively, with a time separation of ~15–20 ns. Furthermore, significant differences in the temporal dynamics of plasma discharges in air and N2 are observed. High levels of excited-state atomic oxygen and NO appear after the initial decay of the N 2 (C) state and coincide primarily with the latter phases of plasma evolution in air environments. From temporal traces of discharge emission, the formation and relaxation timescales of the electronically excited states of N 2 are quantified in pure N2 and air environments with sub-nanosecond resolution. The streak-OES (optical emission spectroscopy) technique enables quantitative time-resolved studies of key chemical species for model validation in ultra-short-pulsed plasmas.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Hydrogen bond arrangements in (H 2 O) 20, 24, 28 clathrate hydrate cages: Optimization and many-body analysis

Here we provide a detailed study of hydrogen bonding arrangements, relative stability, residual entropy, and an analysis of the many-body effects in the (H 2 O) 20 (D-cage), (H 2 O) 24 (T-cage), and (H 2 O) 28 (H-cage) hollow cages making up structures I (sI) and II (sII) of clathrate hydrate lattices. Based on the enumeration of the possible hydrogen bonding networks for a fixed oxygen atom scaffold, the residual entropy (S 0 ) of these three gas phase cages was estimated at 0.754 82, 0.754 44, and 0.754 17 · Nk b , where N is the number of molecules and k b is Boltzmann’s constant. A previously identified descriptor of enhanced stability based on the relative arrangement and connectivity of nearest-neighbor fragments on the polyhedral water cluster [strong-weak-effective-bond model] also applies to the larger hollow cages. The three cages contain a maximum of 7, 9, and 11 such preferable arrangements of trans nearest dimer pairs with one “free” OH bond on the donor molecule (t1d dimers). The Many-Body Expansion (MBE) up to the 4-body suggests that the many-body terms vary nearly linearly with the cluster binding energy. Using a hierarchical approach of screening the relative stability of networks starting from optimizations with the TIP4P, TTM2.1-F, and MB-pol classical potentials, subsequently refining at more accurate levels of electronic structure theory (DFT and MP2), and finally correcting for zero-point energy, we were able to identify a group of four low-lying isomers of the (H 2 O) 24 T-cage, two of which are antisymmetric and the other two form a pair of antipode configurations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Suppressed thermal conductivity in hyperstoichiometric uranium dioxide controlled by phonon lifetimes

Thermal transport in nuclear fuels used for nuclear energy applications is directly tied to performance and reliability. Uranium dioxide (UO 2 ), one of the most important nuclear fuels, can accumulate excess oxygen atoms as interstitial defects, which significantly impacts thermal transport properties. In this study, thermal conductivities and inelastic neutron scattering (INS) measurements on UO 2+ x were performed at low temperatures (2–300K). The thermal conductivity of UO 2+ x (x = 0, 0.03, 0.04, and 0.11) is significantly suppressed compared to UO 2 except near the Néel temperature T N = 30.8 K, where it is independent of x. INS measurements demonstrate that the heat capacities and phonon group velocities of UO 2 and UO 2.08 are similar, and the suppressed thermal conductivity results from smaller phonon lifetimes. These perceptions advance our understanding of thermal transport properties in advanced nuclear fuels and guide safe and economic utilization of nuclear energy.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Polarization-dependent resonant inelastic x-ray scattering of β-Ga2O3: An experimental and computational study

The bulk electronic structure of β-Ga2O3 single crystals was investigated using oxygen K-edge x-ray emission and absorption spectroscopy as well as resonant inelastic soft x-ray scattering. Spectra were obtained for different orientations of the crystal planes with respect to the polarization vector of the incident x-ray beam. The spectra are analyzed with calculations based on density functional theory and using the Bethe–Salpeter equation in the ocean code to take the core–hole interaction into account. These calculations correctly capture all the main features in the experimental spectra, demonstrating the potential of the approach to predict the electronic properties of similar compounds. We find a pronounced anisotropy as a function of the excitation polarization vector and significant differences in the spectral contributions from the inequivalent oxygen atoms of β-Ga2O3.

Pyatenko, Elizaveta↗
DOE OSTI2020

Multidimensional modeling of non-equilibrium plasma generated by a radio-frequency corona discharge

Low-temperature plasma (LTP) ignition concepts rely on the production of radical and charged species to speed up the onset of combustion in spark-ignition engines. These features are responsible for the superior performance of LTP igniters under extremely dilute combustion operation that is not achievable by conventional spark igniters. Additionally, LTP discharges extend the lifetime of the igniters, due to the avoidance of spark processes. For these reasons, the engine research community and the automotive industry have shown growing interest in this technology in the recent years. As of today, computational fluid-dynamics (CFD) codes typically used by the multi-dimensional engine modeling community do not have reliable models to describe LTP ignition processes. One key missing piece of information is the physical and chemical properties of the plasma and their effect on combustion ignition. Most non-equilibrium plasma simulations reported in literature are based on simplified, canonical geometries, with simple discharge excitation schemes. Here we conduct multi-dimensional modeling of the non-equilibrium plasma generated by an application-relevant radio-frequency (RF) corona discharge in air. Three test cases are simulated, characterized by different environmental pressure levels and peak electrode voltage values at room temperature. Streamer penetration, electron number density, atomic oxygen production, and bulk gas temperature distribution in the first 10 sinusoidal pulses are presented and discussed. This model can be used as a key tool for an in-depth understanding of RF-corona discharge for automotive applications and provides the basis for future implementations of dedicated LTP ignition models in CFD codes.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Ion fluxes and memory effects in an Ar–O 2 modulated radiofrequency-driven atmospheric pressure plasma jet

In this work we used molecular beam mass spectrometry to characterize ion fluxes produced by a modulated radiofrequency (RF)-driven atmospheric pressure plasma jet operating in a homogeneous gas environment (Ar + 1% O 2 ). The influence of the RF modulation frequency (100 Hz to 20 kHz) on the ion fluxes was investigated by time-resolved measurements, and the lifetimes of the dominant ions, O 2 + , NO + , O − , O 2 − and O 3 − , were found to be 28 ± 2, 117 ± 8, 7.3 ± 0.4, 17 ± 1 and 23 ± 2 μs, respectively. The absolute ion densities in the near afterglow region were found to be of the order of 1011 cm−3. Significant differences in the dynamics of the positive and negative ions were found; these are explained by the presence of electrons at similar densities in the afterglow produced by electron detachment reactions from negative ions due to the large concentrations of atomic oxygen and singlet delta oxygen. Transitions in ion flux dynamics for different modulation frequencies and at the startup of the plasma were analyzed together with intensified charge coupled device images recording the plasma propagation in order to assess the dynamics of plasma plume propagation and how it is impacted by ‘memory effects’. Quantitative measurements of the ion densities enabling these memory effects are reported. The results in this paper highlight the tremendous impact of memory effects on plasma propagation and the corresponding pre-ionization.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗