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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 1,081 records · Page 60
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Comparison of Computational Strategies for the Calculation of the Electronic Coupling in Intermolecular Energy and Electron Transport Processes

Electronic couplings in intermolecular electron and energy transfer processes calculated by six different existing computational techniques are compared to nonorthogonal configuration interaction for fragments (NOCI-F) results. The paper addresses the calculation of the electronic coupling in diketopyrrolopyrol, tetracene, 5,5'-difluoroindigo, and benzene–Cl for hole and electron transport, as well as the local exciton and singlet fission coupling. NOCI-F provides a rigorous computational scheme to calculate these couplings, but its computational cost is rather elevated. The here-considered ab initio Frenkel–Davydov (AIFD), Dimer projection (DIPRO), transition dipole moment coupling, Michl–Smith, effective Hamiltonian, and Mulliken–Hush approaches are computationally less demanding, and the comparison with the NOCI-F results shows that the NOCI-F results in the couplings for hole and electron transport are rather accurately predicted by the more approximate schemes but that the NOCI-F exciton transfer and singlet fission couplings are more difficult to reproduce.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Revisiting the assignment of atomic charges in metal oxides based on core-level x-ray photoelectron spectra: The case of Ti in SrTiO3(001)

We demonstrate that assigning formal charges to transition metal (TM) cations based on core-level (CL) x-ray photoemission binding energies in oxides leads to physically inconsistent pictures of electronic structure. O 2p–TM 3d hybridization is well known to result in significant covalency in TM–O bonds, thereby reducing TM cation charges from their fully ionic values. However, the ionic bonding model remains the working paradigm for assigning TM CL features, and the resulting cation charges are often taken to be representative of the material under study. Here, we show that a more physically meaningful way to assign charges is to extract information about charge distributions utilizing Dirac–Hartree–Fock theory to calculate CL spectra from first principles and then use the resulting wave functions to determine charges based on orbital occupancies. TM cation charges can also be determined using density functional theory and Bader population analysis. We illustrate these two methods using the Ti 2p spectrum for SrTiO3(001) and show that the agreement between them is excellent. Significantly, the resulting Ti charge is considerably lower than the formal charge. The high degree of similarity between the Ti 2p spectrum for SrTiO3 and those for the rutile and anatase polymorphs of TiO2 suggests that the charge densities surrounding Ti in the latter materials are similar to that in SrTiO3. Taking a broader perspective, oxides containing other first-row transition metals also exhibit covalent character, leading to TM cation charges lower than the analogous fully ionic values in these materials as well.

Chambers, Scott A. (ORCID:000000025415043X)↗
NASA NTRS1991

'Self-consistent' production of ion conics on return current region auroral field lines - A time-dependent, semi-kinetic model

We describe initial results from a time-dependent, semi-kinetic model of plasma outflow incorporating wave-particle interactions along current-carrying auroral field lines. Electrostatic waves are generated by the current driven ion cyclotron instability (CDICI), causing perpendicular velocity diffusion of ions plus electron heating via anomalous resistivity when and where the relative drift between electrons and ions exceeds certain critical velocities. Using the local bulk parameters we calculate these critical velocities, and so are able to self-consistently switch on and off the heating of the various particle species. Due to the dependence of these critical velocities on the bulk parameters of the species the heating effects exhibit quite complex spatial and temporal variations. A wide range of ion distribution functions are observed in these simulations, including conics with energies of a few electron volts and 'ring' distributions. The rings are seen to be a natural result of transverse heating and velocity filter effects and do not require coherent acceleration processes. We also observe the formation of a density depletion in hydrogen and enhanced oxygen densities at high altitudes.

Brown, David G.↗
NASA NTRS1993

Theoretical research program to study chemical reactions in AOTV bow shock tubes

The main focus was the development, implementation, and calibration of methods for performing molecular electronic structure calculations to high accuracy. These various methods were then applied to a number of chemical reactions and species of interest to NASA, notably in the area of combustion chemistry. Among the development work undertaken was a collaborative effort to develop a program to efficiently predict molecular structures and vibrational frequencies using energy derivatives. Another major development effort involved the design of new atomic basis sets for use in chemical studies: these sets were considerably more accurate than those previously in use. Much effort was also devoted to calibrating methods for computing accurate molecular wave functions, including the first reliable calibrations for realistic molecules using full CI results. A wide variety of application calculations were undertaken. One area of interest was the spectroscopy and thermochemistry of small molecules, including establishing small molecule binding energies to an accuracy rivaling, or even on occasion surpassing, the experiment. Such binding energies are essential input to modeling chemical reaction processes, such as combustion. Studies of large molecules and processes important in both hydrogen and hydrocarbon combustion chemistry were also carried out. Finally, some effort was devoted to the structure and spectroscopy of small metal clusters, with applications to materials science problems.

Taylor, Peter R.↗
NASA NTRS1973

Shock-wave structure in a fully ionized gas.

The structure of a steady plane shock in a fully ionized gas has been investigated using the Boltzmann equation with the Gross-Krook type model as the governing equation and the discrete-ordinate method as a tool. The present results agree well with the results obtained by the continuum approach for weak shocks. For strong shocks the present approach gives results that are considerably different from those yielded by the continuum approach, particularly in the high pressure region. Also, the present method gives smooth and continuous shock profiles for high Mach numbers. On the other hand, the results from the continuum approach contain discontinuities in slope. The ion and electron distribution functions across the shock are found to be singly peaked for all cases considered and the effects of the induced electric field is small.

Lu, C. S.↗
DOE OSTI2021

Spin–Orbit Natural Transition Orbitals and Spin-Forbidden Transitions

Natural transition orbitals (NTOs) are in widespread use for visualizing and analyzing electronic transitions. Here, the present work introduces the analysis of formally spin-forbidden transitions with the help of complex-valued spin-orbit (SO) NTOs. The analysis specifically focuses on the components in such transitions that cause their intensity to be non-zero because of SO coupling. Transition properties such as transition dipole moments are partitioned into SO-NTO hole-particle pairs, such that contributions to the intensity from specific occupied and unoccupied orbitals are obtained. The method has been implemented within the restricted active space (RAS) self-consistent field wave function theory framework, with SO coupling treated by RAS state interaction. SO-NTOs have a broad range of potential applications, which is illustrated by the T 2 -S 1 state mixing in pyrazine, spin-forbidden vs. spin-allowed 4f–5d transitions in the Tb 3+ ion, and the phosphorescence of tris(2-phenylpyridine) iridium [Ir(ppy) 3 ].

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

Ionization waves in low-current dc discharges in noble gases obtained with a hybrid kinetic-fluid model

A hybrid kinetic-fluid model is used to study ionization waves (striations) in a low-current plasma column of dc discharges in noble gases. Coupled solutions of a kinetic equation for electrons, a drift-diffusion equation for ions, and a Poisson equation for the electric field are obtained to clarify the nature of plasma stratification in the positive column. A simplified two-level excitation-ionization model is used for the conditions when the nonlinear effects due to stepwise ionization, gas heating, and Coulomb interactions among electrons are negligible. It is confirmed that the nonlocal effects are responsible for the formation of moving striations in dc discharges at low plasma densities and low values of pR (the product of gas pressure and tube radius). Here, the calculated properties of self-excited waves of S–, P–, and R types in neon and S type in argon agree with available experimental data. The reason for helium plasma stability to stratification is clarified. It is shown that sustaining stratified plasma is more efficient than striation-free plasma when the ionization rate is a nonlinear function of the electric field. However, the nonlinear dependence of the ionization rate on the electric field is not required for plasma stratification. Striations of S–, P–, and R types in neon exist with minimal or no ionization enhancement. Effects of the column length and plasma density on the wave properties are demonstrated.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Ytterbium ion trap quantum computing: The current state-of-the-art

In this work, we present an overview of contemporary quantum computing with ytterbium ion traps, placing the emphasis on industry implementations. We provide brief, concrete descriptions of various key features, such as trap loading, electronic structure, qubit function, gates, error analysis, and benchmarking. We focus on the underlying science and current technologies to provide readers with a holistic picture of available techniques for using ytterbium in contemporary ion trap designs.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1968

Nonlinear interactions of electromagnetic waves with a thermally generated cesium plasma.

The interaction of a large‐amplitude disturbing wave with a thermally generated, highly ionized cesium plasma has been investigated using a small‐amplitude sensing wave as a probe. The subsequent interaction between the disturbing and sensing waves is related to the plasma electron temperature. The plasma was contained in a magnetic field of 500–1000 G and had an electron plasma frequency near 10 GHz and an electron gyromagnetic frequency around 2 GHz. The sensing wave was a 10 GHz plane wave of approximately 1.5 mW input power and the disturbing wave was 7.5 GHz plane wave of about 1.2 W peak power. Measurements of the sensing‐wave transmitted power were made using standard microwave techniques. A notch filter in the sensing‐wave receiving circuit reduced the scattered disturbing‐wave interference to an immeasurably low level. Langmuir probes were used to detect disturbing‐wave modulation and to measure plasma temperatures and densities. Measurements of the interaction were correlated with a solution of the Boltzmann transport equation for a perturbed Maxwellian distribution function with binary Coulomb collisions.

Jack G Hewitt, Jr↗
NASA NTRS1985

EMI characteristics of a potential control system

With the development and use of charged particle sources for controlling spacecraft potentials there is a need to better understand the effects of these systems on spacecraft operations. The emission of charged particles perturbs the spacecraft environment and signals are generated which may interfere with other vehicle functions. In particular, the generated signals are apt to interfere with detectors for observing waves that exist naturally in the space environment. Examples of this type of interference are presented from the SCATHA satellite during a period when the vehicle was highly charged. A plasma source on board the spacecraft succeeded in discharging the vehicle with each of four different operating modes. The VLF broadband receiver on SCATHA detected interference over the entire 0-5 kHz range of both the electric and magnetic field detectors during these charged particle emissions. This frequency range includes the 2 kHz electron gyrofrequency but is below the 9 kHz electron plasma frequency. The observations suggest that interference occurs through introduction of anomalous signals, and through suppression of background field measurements.

Donatelli, D. E.↗
NASA NTRS1986

Benchmark full configuration-interaction calculations on H2O, F, and

Full configuration-interaction calculations are reported, and compared to other methods, for H2O at its equilibrium geometry and at two geometries with the H-O bonds stretched. Since the percentage of the self-consistent field (SCF) reference in the full configuration-interaction (FCI) wave function decreases greatly with the bond elongation, the accuracy of techniques based on a single reference do not compare well with the FCI results. However, the results from a complete active space SCF/multireference configuration-interaction (CASSCF/MRCI) treatment are in good agreement with the FCI. Correlation effects in F compared to Ne are far more similar than for Fcompared to Ne, despite F- and Ne being isoelectronic. Since the importance of higher than double excitations is more important for F- than F, a very high percentage of the correlation must be obtained to accurately compute the electron affinity. In a CASSCF/MRCI treatment the higher than quadruple excitations contribute 0.02 eV to the electron affinity (EA), even for modest basis sets.

Bauschlicher, C. W., Jr.↗
NASA NTRS2018

Application of Ab Initio Methods in the Development of Advanced Technical Ceramics

A significant need exists to develop materials not only capable of providing desired electronic and mechanical properties but also survival at extreme temperatures during service and device fabrication, such as co-firing. Computational methods offers an efficient and systematic manner to design new materials and guide their development. As an example computational -based material approaches can be used to determine the suitability of a given materials as a practical thermoelectric for energy harvesting. In this presentation examples are given of applications to relevant technical ceramics such as thermoelectrics, dielectrics, and magnetic systems. The calculation were based on density functional theory and carried out with norm conserving and projector augmented wave (PAW) methods using commercial codes Materials Studio ( Biovia, Inc) with the Cambridge Serial Total Energy Package (CASTEP) and MedeA (Materials Design Inc.) utilizing the Vienna Ab-initio Simulation Package (VASP) as the respective computational engines. This study makes predictions of relevant technical properties of ceramic materials.

thermoelectric↗
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 OSTI2022

The elphbolt ab initio solver for the coupled electron-phonon Boltzmann transport equations

elphbolt is a modern Fortran (2018 standard) code for efficiently solving the coupled electron–phonon Boltzmann transport equations from first principles. Using results from density functional and density functional perturbation theory as inputs, it can calculate the effect of the non-equilibrium phonons on the electronic transport (phonon drag) and non-equilibrium electrons on the phononic transport (electron drag) in a fully self-consistent manner and obeying the constraints mandated by thermodynamics. It can calculate the lattice, charge, and thermoelectric transport coefficients for the temperature gradient and electric fields, and the effect of the mutual electron–phonon drag on these transport properties. The code fully exploits the symmetries of the crystal and the transport-active window to allow the sampling of extremely fine electron and phonon wave vector meshes required for accurately capturing the drag phenomena. The corray feature of modern Fortran, which offers native and convenient support for parallelization, is utilized. The code is compact, readable, well-documented, and extensible by design.

electron drag↗
DOE OSTI2021

Dynamics of Product Branching from Radical Intermediates in Elementary Combustion Reactions (Final Technical Report)

While the total rate constant for many elementary reactions is well-characterized, understanding the product branching in complex reactions presents a formidable challenge. To gain an incisive probe of such reactions, our experiments investigate the dynamics of the product channels that arise from transient radical intermediates along the bimolecular reaction coordinates. Our recent published work uses the methodology developed in my group in the last fifteen years, using both imaging and scattering apparatuses. The experiments generate a particular isomeric form of an unstable radical intermediate along a bimolecular reaction coordinate and study the branching between the ensuing product channels of the energized radical as a function of its internal rotational and vibrational energy under collision-less conditions. The experiments use a combination of: 1) measurement of product velocity and angular distributions in a crossed laser-molecular beam apparatus, with electron bombardment detection in my lab in Chicago or 2) with tunable vacuum ultraviolet photoionization detection at Taiwan's National Synchrotron Radiation Research Center (NSRRC), and 3) velocity map imaging using state-selective REMPI and single photon VUV ionization of radical intermediates and reaction products. We also employ tunable VUV photoionization detection in our imaging apparatus, using difference frequency four-wave mixing to produce photoionization light tunable from 8 to 10.8 eV. This year of support funded our work to photolytically generate the radical intermediate important in the OH + propene reaction when OH adds to an end carbon. Our other major result this past year was on the photoionization detection of vinoxy radicals. Our experiments at the NSRRC definitively show that vinoxy dissociatively ionizes to both CH 3 + and HCO + , and establishes the absolute partial photoionization cross section of vinoxy to CH 3 + at 10.5 and 11.44 eV. This should allow experimentalists detecting vinoxy radicals produced in bimolecular reactions such as OH + propene to get good branching fractions to that product channel. Finally we initiated studies of the photodissociation of 1-bromo-2-chloroethane and 1,1-bromochloroethane at 193 nm at the NSRRC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

Dynamical electrophotoconductivity in polycrystalline thin films

Polycrystalline cadmium sulfide (CdS) films were deposited on lithium niobate (LiNbO3) substrates by vacuum evaporation and annealed to obtain high photosensitivity. The change in photoconductivity of these films due to the penetration of electric fields associated with elastic waves propagating on their substrates was demonstrated and studied. The relationship between the acoustic electric field and the induced change in film conductivity was found to be a nonlinear one. The fractional change in conductivity is strongly dependent on the light intensity and the film temperature, showing a prominent maximum as a function of these quantities. The largest recorded fractional change in conductivity was about 25% at electric fields of the order of 1,000 volts per centimeter. A phenomological model was developed based on the interaction between the space charge created by the electric field and the electron trapping states in the photoconductor.

Kowel, S. T.↗
NASA NTRS1986

Benchmark full configuration-interaction calculations on H2O, F- and F

Full configuration-interaction calculations are reported, and compared to other methods, for H2O at its equilibrium geometry and at two geometries with the H-O bonds stretched. Since the percentage of the self-consistent field (SCF) reference in the full configuration-interaction (FCI) wave function decreases greatly with the bond elongation, the accuracy of techniques based on a single reference do not compare well with the FCI results. However, the results from a complete active space SCF/multireference configuration-interaction (CASSCF/MRCI) treatment are in good agreement with the FCI. Correlation effects in F compared to Ne are far more similar than for F- compared to Ne, despite F- and Ne being isoelectronic. Since the importance of higher than double excitations is more important for F- than F, a very high percentage of the correlation must be obtained to accurately compute the electron affinity. In a CASSCF/MRCI treatment the higher than quadruple excitations contribute 0.02 eV to the electron affinity (EA), even for modest basis sets.

Bauschlicher, C. W., Jr.↗
DOE OSTI2024

Sensing Modalities Deployed - Acoustic

Acoustic approaches to OLM are based on analyzing changes in various forms of pressure waves propagating in solids, fluids or gases. These pressure waves can vary in frequency content from infrasound (seismic events) to the megahertz region (acoustic emissions). A wide variety of commercially available pressure or stain sensing devices are used to make acoustic measurements. These sensors differ in the transduction mechanism used to convert the pressure or strain signal to an electrical output, the sensitivity, dynamic range, bandwidth, directional characteristics, and physical size. All acoustic sensors must be integrated with signal conditioning electronics to convert the sensors’ analog output to discrete digital signals that can then be further analyzed for OLM. Ultimately, the sensing properties listed above will be a function of the sensor transduction mechanism, the sensor design and the conditioning electronics.

47 OTHER INSTRUMENTATION↗