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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Competing Radical and Molecular Channels in the Unimolecular Dissociation of Methylformate

The thermal dissociation of methylformate has been characterized by numerous experimental and theoretical studies that all seem to agree that the lowest energetically accessible process is a 3-center H-atom transfer that leads to the molecular products CH3OH 3 OH + CO. However, these literature studies seem to be at odds with regards to the role of other competing molecular eliminations and bond-fission processes and therefore a complete and resolved mechanistic picture of methylformate thermal dissociation still eludes us. In this work, we have performed high-level electronic structure theory calculations to characterize the energetics of other overlooked molecular and radical processes that can originate on the complex CH3OCHO 3 OCHO potential energy surface (PES). The present calculations do indeed confirm that the lowest energy process accessible on this PES is molecular elimination to form CH3OH 3 OH + CO. However, unlike prior theoretical studies, the present calculations reveal that the second lowest energy process is a 5-center concerted elimination process that leads to the direct formation of H2 2 + CH2O 2 O + CO. We also note that HCO2 2 from the lowest-lying bond fission has two energetically comparable electronic states (of 2 B 2 and 2 A 1 symmetry). Furthermore, the barrier for H-atom migration of CH3OCHO 3 OCHO to form the carbene (CH3OCOH) 3 OCOH) is similar to that for the direct 4-center elimination process leading to CH2O 2 O + CH2O 2 O characterized in prior literature studies. Radical and molecular pathways to CH3 3 + HOCO and CH4 4 + CO2 2 can also be facilitated from this carbene. Master equation calculations were performed to characterize the competition between the various molecular and radical processes on this more elaborate CH3OCHO 3 OCHO PES. The results of the present theoretical analyses were used to resolve outstanding questions on the role of secondary radical- initiated reactions in characterizing prior literature experimental studies.

Chemical Kinetics↗
DOE OSTI2023

Effects of the surface termination and the oxygen vacancy position on LaNiO 3 ultra-thin films: First-principles study

In this study, while ultra-thin layers of the LaNiO 3 film exhibit a remarkable metal-insulator transition as the film thickness becomes smaller than a few unit cell (u.c.), the formation of possible oxygen vacancies and their effects on the correlated electronic structure have been rarely studied using first principles. Here, we investigate the effects of the surface termination and the oxygen vacancy position on the electronic properties and vacancy energetics of LaNiO 3 ultra-thin films under the compressive strain using density functional theory plus U (DFT + U). We find that oxygen vacancies can be easily formed in the Ni layers with the NiO 2 terminated surface (0.5 u.c. and 1.5 u.c. thickness) compared to the structures with the LaO terminated surface and the in-plane vacancy is energetically favored than the out-of-plane vacancy. When two vacancy sites are allowed, the Ni square plane geometry is energetically more stable in most cases as two oxygen vacancies tend to stay near a Ni ion. Strong anisotropy between the in-plane and out-of-plane vacancy formation as well as the layer and orbital dependent electronic structure occur due to strain, surface termination, charge reconstruction, and quantum confinement effects. The in-plane vacancy of the NiO 2 terminated structure is favored since the released charge due to the oxygen vacancy can be easily accommodated in the d x 2 -y 2 orbital, which is less occupied than the d z 2 orbital. Remarkably, the oxygen vacancy structure containing the Ni square-plane geometry becomes an insulating state in DFT + U with a sizable band gap of 1.2 eV because the large crystal field splitting between d z 2 and d x 2 -y 2 orbitals in the square-plane favors an insulating state and the Mott insulating state is induced in other Ni sites due to strong electronic correlations. In the thin-film structure without oxygen vacancies, the strong correlation effect in DFT + U drives a pseudogap ground state at the Fermi energy, similarly as the experimental photo-emission spectra; however, the variation of the DFT + U electronic structure depending on the surface termination becomes weaker compared to those obtained in DFT.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Non-adiabatic quantum interference in the ultracold Li + LiNa → Li 2 + Na reaction

Electronically non-adiabatic effects play an important role in many chemical reactions. However, how these effects manifest in cold and ultracold chemistry remains largely unexplored. Here for the first time we present from first principles the non-adiabatic quantum dynamics of the reactive scattering between ultracold alkali-metal LiNa molecules and Li atoms. We show that non-adiabatic dynamics induces quantum interference effects that dramatically alter the ultracold rotationally resolved reaction rate coefficients. The interference effect arises from the conical intersection between the ground and an excited electronic state that is energetically accessible even for ultracold collisions. These unique interference effects might be exploited for quantum control applications such as a quantum molecular switch. The non-adiabatic dynamics are based on full-dimensional ab initio potential energy surfaces for the two electronic states that includes the non-adiabatic couplings and an accurate treatment of the long-range interactions. A statistical analysis of rotational populations of the Li2 product reveals a Poisson distribution implying the underlying classical dynamics are chaotic. The Poisson distribution is robust and amenable to experimental verification and appears to be a universal property of ultracold reactions involving alkali metal dimers.

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

Electronic Excitation Response of DNA to High-Energy Proton Radiation in Water

The lack of molecular-level understanding for the electronic excitation response of DNA to charged particle radiation, such as high-energy protons, remains a fundamental scientific bottleneck in advancing proton and other ion beam cancer therapies. In particular, the dependence of different types of DNA damage on high-energy protons represents a significant knowledge void. Here, in this work, we employ first-principles real-time time-dependent density functional theory simulation, using a massively parallel supercomputer, to unravel the quantum-mechanical details of the energy transfer from high-energy protons to DNA in water. The calculations reveal that protons deposit significantly more energy onto the DNA sugar-phosphate side chains than onto the nucleobases, and greater energy transfer is expected onto the DNA side chains than onto water. As a result of this electronic stopping process, highly energetic holes are generated on the DNA side chains as a source of oxidative damage.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

An Ab Initio Electronic Structure Investigation of the Ground and Excited States of ScH + , YH + , and LaH +

Multireference configuration interaction (MRCI), Davidson-corrected MRCI (MRCI+Q), coupled-cluster singles, doubles, and perturbative triples [CCSD(T)], and frozen-core full configuration interaction (fcFCI) calculations were carried out using large, correlation-consistent basis sets to investigate the excited states of the Sc atom and the spin–free and spin–orbit coupled potential energy profiles, energetics, spectroscopic constants, and electron populations of low-lying states of MH + (M = Sc, Y, La). The core electron correlation effects, complete basis set effects, and spin–orbit coupling effects were also evaluated. The first four electronic states of all MH + are 1 2 Δ, 1 2 Σ + , 1 2 Π, and 2 2 Σ + with 1σ 2 1δ 1 , 1σ 2 2σ 1 , 1σ 2 1π 1 , and 1σ 2 3σ 1 single-reference electron configurations, respectively. These states of MH + can be represented by the M 2+ H – ionic structure. The ground states of ScH + , YH + , and LaH + are 1 2 Δ 3/2 , 1 2 Σ + 1/2 , and 1 2 Δ 3/2 with 55.45, 60.54, and 62.34 kcal/mol bond energies, respectively. The core electron correlation was found to be vital for gaining accurate predictions on the ground and excited state properties of MH + . The spin–orbit coupling effects are minor for ScH + but become substantial moving to YH + and LaH + . Overall, the results of this work are in good agreement with the limited set of experimental findings of MH + available in the literature and will be of use for future investigations. Furthermore, the theoretical approaches, findings, and trends reported here are expected to aid studies of similar species.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Outer Radiation Belt Flux and Phase Space Density Response to Sheath Regions: Van Allen Probes and GPS Observations

Turbulent and compressed sheath regions preceding interplanetary coronal mass ejections strongly impact electron dynamics in the outer radiation belt. Changes in electron flux can occur on timescales of tens of minutes, which are unlikely to be captured by a two-satellite mission. The recently released Global Positioning System (GPS) data set generally has shorter revisit times (at L ~ 4–8) owing to the large number of satellites in the constellation equipped with energetic particle detectors. Investigating electron fluxes at energies from 140 keV to 4 MeV and sheaths observed in 2012–2018, we show that the flux response to sheaths on a timescale of 6 hr, previously reported from Van Allen Probes (RBSP) data, is reproduced by GPS measurements. Furthermore, GPS data enables derivation of the response on a timescale of 30 min, which further confirms that the energy and L-shell dependent changes in electron flux are associated with the impact of the sheath. Sheath-driven loss is underestimated over longer timescales as the electrons recover during the ejecta. We additionally show the response of electron phase space density (PSD), which is a key quantity in identifying non-adiabatic loss from the system and electron energization through wave-particle interactions. The PSD response is calculated from both RBSP and GPS data for the 6 hr timescale, as well as from GPS data for the 30 min timescale. The response is divided based on the geoeffectiveness of the sheaths revealing that electrons are effectively accelerated only during geoeffective sheaths, while loss commonly occurs during all sheaths.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

Thorium Monosilicide, ThSi: An Experimental and Theoretical Study

The present theoretical and experimental combination study investigates the ThSi molecule in detail. Computationally, we utilized high-level multireference and coupled-cluster levels of theory conjoined with large correlation consistent basis sets to study a series of electronic and spin–orbit states of ThSi. Here, we report potential energy curves (PECs), electron configurations at equilibrium distances, spectroscopic constants, energetics, and spin–orbit coupling effects for 16 electronic states of ThSi. The studied 16 electronic states are arranged tightly within 0.9 eV, highlighting the complexity of the electronic spectrum of ThSi. The ground electronic state of ThSi is a single-reference 1 1 Σ + state that derives from the 1σ 2 2σ 2 1π 4 electronic configuration. The Ω = 0 + spin–orbit ground state of ThSi is composed of 1 1 Σ + (47%) and 13Π (44%) electronic states. Our measured bond energy (D0) of ThSi, obtained using resonant two-photon ionization (R2PI) spectroscopy is 3.146(4) eV, where the assigned error limit is given in parentheses in units of the last quoted digits. The computed D0 of ThSi (Ω = 0 + ) at the CBS-C-CCSD(T)-δT(Q)-δDK-δSO level (3.181 eV) is in good agreement with the experimental value. Our derived enthalpy of formation for ThSi, Δ f H 0K o (ThSi(g)), is 971.8(6.0) kJ/mol. Finally, we have performed density functional theory (DFT) calculations for ThSi(1 1 Σ + ) using 16 exchange correlation functionals that span multiple rungs of “Jacob’s ladder” of density functional approximation (DFA) to assess the DFT errors on D 0 , r e , and ω e of ThSi with respect to experimental and ab initio coupled-cluster values.

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

An Introduction to Radiation Damage in Minerals and Ceramics [Slides]

Radiation effects in minerals and ceramics are quite distinct from effects observed in metals. This is largely due to interactions between radiation and the electronic structure of insulating materials that are unique compared to metallic conductors. Most notably, insulators exhibit property changes when energetic particles lose energy to electrons in the solid, whereas metals are unaffected by electronic energy losses. In addition, displacive radiation damage effects (atoms being knocked off their lattice sites by energetic particles) are much more complex in insulators, due to the complexities of their crystal structures (multiple cation and anion sublattices). In this presentation, we will focus on the atomistic mechanisms responsible for radiation damage in minerals and ceramics, when energetic particles lose energy while penetrating a solid. We will consider several examples, including (i) irradiation induced color center formation in gemstones; (ii) latent defects in alkali halides (relevance to thermoluminescent detectors); (iii) radioactive decay-induced amorphization of natural minerals; and (iv) extended defect formation and phase stability in complex oxides.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Effect of doping on the phase stability and superconductivity in LaH 10

Here, we present a computational investigation into the effects of chemical doping with 15 different elements on phase stability and superconductivity in the LaH 10 structure. Most doping elements were found to induce softening of phonon modes, enhancing electron-phonon coupling and improving critical superconducting temperature while weakening dynamical stability. Unlike these dopants, Ce was found to extend the range of dynamical stability for LaH 10 by eliminating the Van Hove singularity near the Fermi level. The doped compound, La 0.75 Ce 0.25 H 10 , maintains high-temperature superconductivity. We also demonstrate that different Ce doping configurations in the LaH 10 structure have a minimal effect on energetic stability and electron-phonon coupling strength. Our findings suggest that Ce is a promising dopant to stabilize LaH 10 at lower pressures while preserving its high-temperature superconductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Ab Initio Dynamics of Graphene and Graphyne Electrodes in Vacuum and in the Presence of Electrolytes

Graphene and graphyne electrodes are both relevant for electrochemical energy storage applications due to their unique physical, chemical, and electronic properties. Graphyne has been considered even more attractive than graphene due to its larger specific surface area, greater electronic mobility, and intrinsic band gap. The analyses presented in this work reveal relevant features of graphyne in an interaction with an electrolyte that can be useful for practical applications. Although there is already a considerable volume of work on graphyne, the analysis of its properties taking into account the dynamics of its network and the interaction with the condensed medium has not yet been presented. Here, ab initio molecular dynamics simulations were performed to study the energetic, structural, spectroscopic, and electronic properties of graphene and graphyne electrodes in vacuum and in the presence of an electrolyte (EMIM-BF 4 ). A detailed analysis of the electrode–electrolyte interaction is reported for both systems. Structural features are presented in terms of both radial and spatial distribution functions and angular orientation distributions. Power spectral analyses and molecular orbital maps provided important insights into the intermolecular interactions in graphene and graphyne systems, describing the main differences as well as revealing similarities between them.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Influence of Surface Ligands on Energetics at FASnI 3 /C 60 Interfaces and Their Impact on Photovoltaic Performance

Interfacial chemistry and energetics significantly impact the performance of photovoltaic devices. In the case of Pb-containing organic metal halide perovskites, photoelectron spectroscopy has been used to determine the energetic alignment of frontier electronic energy levels at various interfaces present in the photovoltaic device. For the Sn-containing analogues, which are less toxic, no such measurements have been made. Through a combination of ultraviolet, inverse, and X-ray photoelectron spectroscopy (UPS, IPES, and XPS, respectively) measurements taken at varying thickness increments during stepwise deposition of C 60 on FASnI 3 , we present the first direct measurements of the frontier electronic energy levels across the FASnI 3 /C 60 interface. The results show band bending in both materials and transport gap widening in FASnI 3 at the interface with C 60 . The XPS results show that iodide diffuses into C 60 and results in n-doping of C 60 . This iodide diffusion out of FASnI 3 impacts the valence and conduction band energies of FASnI 3 more than the core levels, with the core level shifts displaying a different trend than the valence and conduction bands. Surface treatment of FASnI 3 with carboxylic acids and bulky ammonium substituted surface ligands results in slight alterations in the interfacial energetics, and all surface ligands result in similar or improved PV performance relative to the untreated devices. Finally, the greatest PV stability results from treatment with a fluorinated carboxylic acid derivative; however, iodide diffusion is still observed to occur with this surface ligand.

interfacial energetics↗
DOE OSTI2025

A dynamic protein interactome drives energy conservation and electron flux in Thermococcus kodakarensis

ABSTRACT Life is supported by energy gains fueled by catabolism of a wide range of substrates, each reliant on the selective partitioning of electrons through redox ( red uction and ox idation) reactions. Electron flux through tunable and regulated protein interactions provides dynamic routes for energy conservation, but how electron flux is regulated in vivo , particularly for archaeal metabolisms that support rapid growth at the thermodynamic limits of life, is poorly understood. Identification of bona fide in vivo protein assemblies and how such assemblies dictate the totality of electron flux is critical to our understanding of the regulation imposed on metabolism, energy production, and energy conservation. Here, 25 key proteins in central metabolic redox pathways in the model, genetically accessible, hyperthermophilic archaeon Thermococcus kodakarensis , were purified to reveal an extensive, dynamic, and tightly interconnected network of protein interactions that responds to environmental cues (such as the availability of various reductive sinks) to direct electron flux to maximize energetic gains. Interactions connecting disparate functions suggest many catabolic and anabolic activities occur in spatial proximity in vivo , and while protein complexes have been historically defined under optimal conditions, many of these complexes appear to maintain alternative partnerships in changing conditions. The totality of the results obtained redefines our understanding of in vivo assemblies driving ancient metabolic strategies supporting the growth of modern Archaea. IMPORTANCE Given the potential for rational genetic manipulations of biofuel- and biotech-promising archaea to yield transformative results for major markets, it is a priority to define how the metabolisms of such species are controlled, at least in part, by in vivo protein assemblies, and from such, define routes of energy flux that can be most efficiently altered toward biofuel or biotechnological gains. Proteinaceous electron carriers (PECs, such as ferredoxins) offer the potential for specific protein–protein interactions to coordinate selective reductive flow. Employing the model, genetically accessible, hyperthermophilic archaeon, Thermococcus kodakarensis , we establish the metabolic protein interactome of 25 key redox proteins, revealing that each redox active protein has a dynamic partnership profile, suggesting catabolic and anabolic activities may occur in concert and in temporal and spatial proximity in vivo . These results reveal critical importance in evaluating the newly identified partnerships and their role and utility in providing regulated redox flux in T. kodakarensis .

Williams, Sere A. (ORCID:0000000235509590)↗
DOE OSTI2021

Non-radiative luminescence decay with self-trapped hole migration in strontium titanate: Interplay between optical and transport properties

A novel model for the non-radiative decay of self-trapped excitons (STEs) in the advanced functional oxide SrTiO3 is proposed and supported by experimental observations. The study is based on the initial ionoluminescence stage for STE emission at 2.5 eV, and its dependence on temperature and electronic excitation rate under energetic heavy-ion irradiation. For all temperatures, this initial stage reaches rapidly a quasi-steady level, and then decreases as induced-structural damage increases. The quasi-steady luminescence exhibits a linear dependence on the excitation rate, suggesting a constant efficiency for STEs formation. An activation energy of 55 meV, essentially independent of the incident ion mass and energy of projectile-ion, is deduced from an Arrhenius-type relationship with irradiation temperature. This energy is in good agreement with experimental values, measured for non-radiative STE decay under ns-laser pulse excitation, and reasonably consistent with density functional theory calculations for migration of self-trapped holes (STHs) described by a small-polaron adiabatic hopping model. A new mechanism dealing with a non-radiative contribution to the STE transition is discussed, consisting of STH migration through thermally-activated hopping and annihilation with the STE-electron. Luminescence kinetics from the chromium intrinsic impurity strongly supports this model, being consistent with the annihilation of Cr 3+ centers through recombination with migrating STHs.

luminescence↗
DOE OSTI2025

Resolving the phase of Fano resonance wave packets with photoelectron frequency-resolved optical gating

The creation of structured electronic wave packets (EWPs) energetically close to Fano resonances has been achieved with ultrafast extreme ultraviolet coherent light sources. However, direct real-time observations of EWP evolution and full reconstructions of the quantum properties of EWPs, including both amplitude and phase, are lacking. Here we introduce and demonstrate a comprehensive approach for the direct measurement and complete characterization of structured EWPs created within a prototypical Fano resonance. Because of its analogy with frequency-resolved optical gating (FROG), we named the method photoelectron FROG. The correlated EWP is initiated by a carefully engineered extreme UV pump pulse. A weak near-infrared laser field, serving as a probe pulse, samples the evolution of the EWPs in the time domain, as well as in the frequency domain. The amplitude and phase of the EWPs are obtained via a time-dependent reconstruction algorithm based on a short-time Fourier transformation. Given the excellent agreement between our experimental results and time-dependent reconstructions, we expect this method to be broadly applicable to the study of ultrafast processes, especially electronic ones, in complex systems, as well as the coherent control of such systems on their fundamental timescales.

quantum optics↗
DOE OSTI2020

Photocathodes

Photocathodes were at the heart of quantum physics development in the early twentieth century and are still used in high technologies devices like night-vision goggles, photomultiplier tubes and particle accelerators. The simplest form of photocathode is a metallic surface,negatively biased,from which electrons are extracted by energetic photons. After a brief description of the photocathode preparation, this chapter will present the latest developments and limitations of metallic and semiconductor photocathodes.

Liu, Wei↗
DOE OSTI2022

Electrochemical Structure of the Plasma–Liquid Interface

Nonthermal atmospheric pressure plasma in contact with a liquid yields a variety of energetic photons, ions, and electrons, which can be transported into the plasma–liquid interface (PLI). Similar to the electrochemical interface formed between a solid electrode and electrolyte in conventional electrochemical systems, the charge-transfer process across the PLI is able to promote reduction–oxidation (redox) reactions. However, in the case of free plasma jets in contact with liquids, the absence of solid electrodes obscures the spatial locations of the electrochemical half-reactions. Herein, we present a spatial electrochemical measurement technique used to characterize an aqueous solution in contact with an atmospheric pressure plasma jet. The technique is based on measuring the potential difference between two identical Ag/AgCl electrochemical electrodes positioned at different locations within the solution. More specifically, electrochemical maps were made by measuring the potential of one electrochemical electrode positioned at different locations near the PLI with respect to the other electrochemical electrode positioned far away from the PLI in the bulk solution. Regions in the map with negative and positive potential differences between these electrochemical electrodes were used to identify the electrodeless cathode and anode, respectively. Here, visualization of the spatial distribution of molecular colorimetric redox indicators by multispectral imaging revealed that reduction was occurring near the plasma jet centerline while oxidation was occurring further away in solution, which constitutes an independent confirmation of the electrochemical maps.

Absorption↗
DOE OSTI2025

Evidence for I 2 loss from the perovskite–gas interface upon light-induced halide segregation

Sunlight-induced halide segregation in (CH 3 NH 3 )Pb(Br x I 1−x ) 3 (1 > x > 0.2), which limits obtainable voltages from solar cells with these perovskite absorbers, reverses upon resting in the dark. However, sustained illumination at ca. 1 sun opens a new decomposition pathway, leading to irreversible I 2 loss in an open system. We conclusively show I 2 off-gassing from halide-segregated (CH 3 NH 3 )Pb(Br 0.75 I 0.25 ) 3 by trapping gaseous I 2 and tracking the electronic conductivity of the perovskite, which increases from electron-doping as iodides are oxidized to iodine. Importantly, we show that this reaction occurs across the perovskite-air solid–gas interface, without confounding effects from solvent or reactive solid interfaces. This characterization was conducted under a nitrogen atmosphere, avoiding vacuum- and oxygen-driven I 2 loss pathways. Consistent observations of I 2 loss upon light-soaking CsPb(Br 0.75 I 0.25 ) 3 films show that this reaction is intrinsic to the inorganic framework. We propose that the disruption of iodide-rich domains in the halide-segregated films through I 2 loss can masquerade as a light-induced healing or apparent remixing of the segregated film, when in fact it leads to irreversible decomposition. Although I 2 off-gassing is less likely in bromide-rich solid solutions, light-induced halide segregation brings the iodides into proximity and forms electronic states that are energetically poised to trap and accumulate holes, providing a driving force for I 2 loss. Thus, even bromide-rich mixed-halide perovskite absorbers will benefit from I 2 -impermeable encapsulation for long-term stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗