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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 901 records · Page 50
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Coupled Electronic and Nuclear Motions during Azobenzene Photoisomerization Monitored by Ultrafast Electron Diffraction

Ultrafast electron diffraction is a powerful technique that can resolve molecular structures with femtosecond and angstrom resolutions. We demonstrate theoretically how it can be used to monitor conical intersection dynamics in molecules. Specific contributions to the signal are identified which vanish in the absence of vibronic coherence and offer a direct window into conical intersection paths. A special focus is on hybrid scattering from nuclei and electrons, a process that is unique to electron (rather than X-ray) diffraction and monitors the strongly coupled nuclear and electronic motions in the vicinity of conical intersections. Furthermore, an application is made to the cis to trans isomerization of azobenzene, computed with exact quantum dynamics wavepacket propagation in a reactive two-dimensional nuclear space.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Electronic Energies Are Not Enough: An Ion Mobility-Aided, Quantum Chemical Benchmark Analysis of H + GPGG Conformers

Peptides and proteins exist not as single, lowest energy structures but as ensembles of states separated by small barriers. In order to study these species we must be able to correctly identify their gas phase conformational distributions, and ion mobility spectrometry (IMS) has arisen as an experimental method for assessing the gas phase energetics of flexible peptides. Here, we present a thorough exploration and benchmarking of the low energy conformers of the small, hairpin peptide H+ GPGG with the aid of ion mobility spectrometry against a wide swath of density functionals (35 dispersion-corrected and uncorrected functionals represented by 21 unique exchange–correlation functionals) and wave function theory methods (15 total levels of theory). The three experimentally resolved IMS peaks were found to correspond to three distinct pairs of conformers, each pair composed of species differing only by the chair or boat configuration of the proline. Two of the H+ GPGG conformer pairs possess a cis configuration about the Pro–Gly1 peptide bond while the other adopts a trans configuration. While the experimental spectrum reports a higher intensity for the cis-1 conformer than the trans conformer, 13 WFT levels of theory, including a complete basis set CCSD(T) extrapolation, obtain trans to be favored in terms of the electronic energy. This same effect is seen in 14 of the 18 dispersion-corrected density functionals studied, whereas the remaining 17 functionals show more variety. Only when Gibbs free energies are considered do the WFT methods and dispersion-corrected functionals reflect the experimental distribution. CAM-B3LYP-D3BJ emerges as the best-performing density functional, matching the experimental distribution and the CCSD(T)/CBS relative energies within 6%. Further analysis reveals the trans conformer to be favored electronically, but entropically disfavored, leading to the experimental preference of the cis-1 conformer. Furthermore, these results highlight the danger in considering only the electronic energies, which is common practice in electronic structure theory predictions of conformational energy distributions. Additionally, the effects of temperature and scaling of the frequencies used in obtaining the Gibbs free energies are explored.

Energy↗
DOE OSTI2020

Electron Affinity and Electronic Structure of Hexafluoroacetone (HFA) Revealed by Photodetaching the [HFA] •– Radical Anion

A great deal of effort has been focused on developing a metal-free catalytic system for epoxidation of unreactive alkenes. Fluoroketones are thought as remarkably promising catalysts for epoxidation reactions. The combination of fluorinated alcohols and catalytic amounts of hexafluoroacetone (HFA) gives a versatile and effective medium for epoxidation of various olefins with hydrogen peroxide. However, the fundamental physicochemical properties of HFA remained largely unclear, although they were very important to understand the related interactions. Here, in this study, we performed a joint study on the electron affinity and electronic structure of HFA employing negative ion photoelectron (NIPE) spectroscopy and quantum chemistry calculations. Two distinct bands with complicated vibrational progressions were observed in the 193 nm NIPE spectrum. The adiabatic/vertical detachment energies (ADE/VDE) were derived to be 1.42/2.06 and 4.43/4.86 eV for the ground singlet state and excited triplet state, respectively. Using the optimized geometries and vibrational frequencies of the anion and the neutral, the Franck–Condon factors were calculated for electron detachments to produce HFA in its lowest singlet and triplet states. Good agreements are obtained hereby for both bands between the experimental and calculated NIPE spectra, when taking into account combination vibrational excitations, unequivocally revealing that HFA possesses a singlet ground state with a giant singlet–triplet energy difference (ΔE ST ). The electron affinity (EA) and ΔE ST of HFA were therefore determined to be EA = 1.42 ± 0.02 eV and ΔE ST = −3.01 eV.

Wang, Lei↗
DOE OSTI2021

The Low-Lying Electronic States of NO 2 : Potential Energy and Dipole Surfaces, Bound States, and Electronic Absorption Spectrum

Nitrogen dioxide, NO 2 , is a free radical composed of the two most abundant elements in Earth’s atmosphere, nitrogen and oxygen, and is relevant to atmospheric and combustion chemistry. The electronic structure of even its lowest-lying states is remarkably complex, with various conical intersections and Renner–Teller pairings, giving rise to complex and perturbed vibronic states. Here we report some analysis of the 18 molecular states of doublet spin-multiplicity formed by combining ground-state N( 4 S u ) and O( 3 P g ) atoms. In this work, three-dimensional potential energy surfaces were fit at the MRCI(Q)-F12/VTZ-F12 level, describing the lowest four ($\tilde X$, $\tilde A$, $\tilde B$, and $\tilde C$) electronic states. A properties-based diabatization procedure was applied to accommodate the intersections, producing energies in a quasidiabatic representation and yielding couplings that were also fit into surfaces. The low-lying vibrational levels on the ground $\tilde X$ state were computed and compared with experimental measurements. Compared to experiment, the lowest 125 calculated vibrational levels (up to 8500 cm –1 above the zero-point energy) have a root-mean-squared error of 16.5 cm –1 . In addition, dipole moments for each of the lowest four electronic states—and the transition dipoles between them—were also computed and fit. With the coupled energy and dipole surfaces, the electronic spectrum was calculated in absolute intensity and compared with experimental measurements. Detailed structure in the experimental spectrum was successfully reproduced, and the total integrated intensity matches experiment to an accuracy of ~1.5% with no empirical adjustments.

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

Revised M11 Exchange-Correlation Functional for Electronic Excitation Energies and Ground-State Properties

The ability of Kohn-Sham density functional theory (KS-DFT) to accurately predict various types of electronic excitation energies with (necessarily approximate) exchange-correlation functionals faces several challenges. Chief among these is that valence excitations are usually inherently multiconfigurational and therefore best treated by functionals with local exchange, whereas Rydberg and charge transfer excitations are often better treated with nonlocal exchange. The question arises of whether one can optimize a functional such that all three kinds of excitations (valence, Rydberg, and charge transfer – including long-range charge transfer) are treated in a balanced and accurate way. The goal of the present work is to try to answer that question and then to optimize a functional with the best possible balanced behavior. Of the variety of functional types available, we select range-separated hybrid meta functionals because (i) range separation allows the percentage of Hartree–Fock (HF) exchange to change with interelectronic separation, and therefore, one can have 100% HF exchange at large interelectronic separations, which gives good performance for long-range charge-transfer excitations, while the range separation allows one to simultaneously have smaller values of HF exchange at small and intermediate inter-electronic separations, which give good performance for valence and Rydberg excitations and (ii) meta functionals allow one to obtain better accuracy with high HF exchange than is possible with functionals whose local part depends only on spin densities and their gradients. Furthermore, this work starts with the range-separated hybrid meta functional, M11, and re-optimizes it (with stronger smoothness restraints) against electronic excitation energies and ground-state properties to obtain a new functional called revM11 that gives good performance for all three types of electronic excitations and at the same time gives very good predictions across-the-board for ground-state properties.

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

Effect of Electronic Coupling on Electron Transfer Rates from Photoexcited Naphthalenediimide Radical Anion to Re(bpy)(CO) 3 X

The electron transfer rate between a donor and an acceptor depends on the free energy change for the reaction as well as differences in structure and electronic coupling between the initial and final states. Selective excitation of a naphthalenediimide radical anion (NDI•–) covalently linked at the 4-, 5-, or 6-positions of the bipyridine (bpy) in the Re(bpy)(CO) 3 X (X = Cl or pyridine) carbon dioxide reduction catalyst results in electron transfer from 2* NDI •– to Re(bpy)(CO) 3 X to form Re(bpy•–)(CO) 3 X, the first intermediate in the photocatalytic reduction of CO 2 . Femtosecond UV/vis, near-IR, and mid-IR spectroscopy on these constitutional isomers and a set of appropriate reference molecules show that systematically varying the electronic coupling as well as the reaction free energy increases the lifetime of Re(bpy•–)(CO) 3 X by an order of magnitude when the NDI chromophore is attached to the 6-position of bpy. NMR and X-ray structural studies along with computational modeling are used to identify the conformation of Re(6-NDI-bpy)(CO) 3 X responsible for these favorable changes. Extending the lifetime of the reduced complex in the covalent photosensitizer–catalyst assembly is a critical requirement for the photocatalytic CO 2 reduction and artificial photosynthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Electronic Interactions in the Bacterial Reaction Center Revealed by Two-Color 2D Electronic Spectroscopy

The bacterial reaction center (BRC) serves as an important model system for understanding the charge separation processes in photosynthesis. Knowledge of the electronic structure of the BRC is critical for understanding its charge separation mechanism. While it is well-accepted that the "special pair" pigments are strongly coupled, the degree of coupling among other BRC pigments has been thought to be relatively weak. Here we study the W(M250)V mutant BRC by two-color two-dimensional electronic spectroscopy to correlate changes in the Q(x) region with excitation of the Q(y) transitions. The resulting Q(y)-Q(x) cross-peaks provide a sensitive measure of the electronic interactions throughout the BRC pigment network and complement one-color 2D studies in which such interactions are often obscured by energy transfer and excited-state absorption signals. Our observations should motivate the refinement of electronic structure models of the BRC to facilitate improved understanding of the charge separation mechanism.

Konar, Arkaprabha↗
DOE OSTI2017

Design of Heterogeneous Chalcogenide Nanostructures with Pressure-Tunable Gaps and without Electronic Trap States

Heterogeneous nanostructures, such as quantum dots (QDs) embedded in solid matrices or core–shell nanoparticles, are promising platforms for a wide variety of applications, including phosphors with increased quantum yield, photocatalysis, and solar energy conversion. However, characterizing and controlling their interfacial morphology and defects, which greatly influence their electronic properties, have proven difficult in numerous cases. Here we carried out atomistic calculations on chalcogenide nanostructured materials, i.e., PbSe QDs in CdSe matrices and CdSe embedded in PbSe, and we established how interfacial and core structures affect their electronic properties. In particular, we showed that defects present at interfaces of PbSe nanoparticles and CdSe matrices give rise to detrimental intragap states, degrading the performance of photovoltaic devices. Instead, the electronic gaps of the inverted system (CdSe dots in PbSe) are clean, indicating that this material has superior electronic properties for solar applications. In addition, our calculations predicted that the core structure of CdSe and in turn its band gap may be tuned by applying pressure to the PbSe matrix, providing a means to engineering the properties of new functional materials.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Inorganic “Conductive Glass” Approach to Rendering Mesoporous Metal–Organic Frameworks Electronically Conductive and Chemically Responsive

A representative mesoporous metal–organic-framework (MOF) material, NU-1000, has been rendered electronically conductive via a robust inorganic approach that permits retention of MOF crystallinity and porosity. The approach is based on condensed-phase grafting of molecular tin species onto the MOF nodes via irreversible reaction with hydroxyl and aqua ligands presented at the node surface, a self-limiting process termed solvothermal installation (of metal ions) in MOFs (SIM, a solution-phase analog of atomic layer deposition in MOFs). Treatment of the modified MOF with aerated steam at 120 °C converts the grafted tin molecules to tetratin(IV)oxy clusters, with the clusters being sited between insulating pairs of zirconia-like nodes (the zirconium component being key to endowing the parent material with requisite chemical and thermal stability). By introducing new O–H presenting ligands on the modified-MOF node, the high-temperature steam step additionally serves to reset the material to reactive form, thus enabling a second self-limiting tin-grafting step to be run (and after further steam treatment, enabling a third). Difference-envelop-density (DED) analyses of synchrotron-derived X-ray scattering data, with and without installed tin species, show that the clusters formed after one cycle are spatially isolated, but that repetitive SIM cycling adds metal and oxygen ions in a way that enshrouds nodes, links clusters, and yields continuous one-dimensional strands of oxy-tin(IV), oriented exclusively along the c axis of the MOF. Two-probe conductivity measurements show that the parent MOF and the version containing isolated oxy-tin(IV) clusters are electrically insulating, but that the versions featuring continuous strands show an electrical conductivity of 1.8 × 10–7 S/cm after three Sn-SIM cycles. When combined with interdigitated microelectrodes, the solvent-free and conductive-glass-modified material (three Sn-SIM cycles) displays a substantial and persistent increase in electrical conductivity during exposure to 5% H2, indicating a role for dissociated H2 as an electronic dopant. The increase can be repetitively reversed by alternating H2 with air, illustrating the ability of the conductive MOF to function as a resistive sensor for H2 and suggesting further potential applications that may capitalize on the combination of high volumetric surface area, high mesoporosity, high chemical and thermal stability, and significant electrical conductivity.

bio-inspired↗
DOE OSTI2015

Role of Quinones in Electron Transfer of PQQ–Glucose Dehydrogenase Anodes—Mediation or Orientation Effect

In this study, the influence of two quinones (1,2- and 1,4-benzoquinone) on the operation and mechanism of electron transfer in PQQ-dependent glucose dehydrogenase (PQQ–sGDH) anodes has been determined. Benzoquinones were experimentally explored as mediators present in the electrolyte. The electrochemical performance of the PQQ–sGDH anodes with and without the mediators was examined and for the first time molecular docking simulations were used to gain a fundamental understanding to explain the role of the mediator molecules in the design and operation of the enzymatic electrodes. It was proposed that the higher performance of the PQQ–sGDH anodes in the presence of 1,2- and 1,4-benzoquinones introduced in the solution is due to the shorter distance between these molecules and PQQ in the enzymatic molecule. It was also hypothesized that when 1,4-benzoquinone is adsorbed on a carbon support, it would play the dual role of a mediator and an orienting agent. At the same time, when 1,2-benzoquinone and ubiquinone are adsorbed on the electrode surface, the enzyme would transfer the electrons directly to the support, and these molecules would primarily play the role of an orienting agent.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2018

Charge Delocalization and Bulk Electronic Conductivity in the Mixed-Valence Metal–Organic Framework Fe(1,2,3-triazolate) 2 (BF 4 ) x

Metal–organic frameworks are of interest for use in a variety of electrochemical and electronic applications, although a detailed understanding of their charge transport behavior, which is of critical importance for enhancing electronic conductivities, remains limited. Herein, we report isolation of the mixed-valence framework materials, Fe(tri) 2 (BF 4 ) x (tri – = 1,2,3-triazolate; x = 0.09, 0.22, and 0.33), obtained from the stoichiometric chemical oxidation of the poorly-conductive iron(II) framework Fe(tri) 2 , and find that the conductivity increases dramatically with iron oxidation level. Notably, the most oxidized variant, Fe(tri) 2 (BF 4 ) 0.33 , displays a room-temperature conductivity of 0.3(1) S/cm, which represents an increase of eight orders of magnitude from that of the parent material and is one of the highest conductivity values reported among three-dimensional metal–organic frameworks. Detailed characterization of Fe(tri) 2 and the Fe(tri) 2 (BF 4 ) x materials via powder X-ray diffraction, Mössbauer spectroscopy, and IR and UV-vis-NIR diffuse reflectance spectroscopies reveals that the high conductivity arises from intervalence charge transfer between mixed-valence low-spin Fe II/III centers. Further, Mössbauer spectroscopy indicates the presence of a valence-delocalized Fe II/III species in Fe(tri) 2 (BF 4 ) x at 290 K, one of the first such observations for a metal–organic framework. The electronic structure of valence-pure Fe(tri) 2 and the charge transport mechanism and electronic structure of mixed-valence Fe(tri) 2 (BF 4 ) x frameworks are discussed in detail.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Dynamics of Back Electron Transfer in Dye-Sensitized Solar Cells Featuring 4-tert-Butyl-Pyridine and Atomic-Layer-Deposition Alumina as Surface Modifiers.

A series of dye-sensitized solar cells (DSCs) was constructed with TiO2 nanoparticles and N719 dye. The standard I-3(-)/I- redox shuttle and the Co(1,10-phenanthroline)(3)(3+/2+) shuttle were employed. DSCs were modified with atomic-layered-deposited (ALD) coatings of Al2O3 and/or with the surface-adsorbing additive 4-tert-butyl-pyridine. Current-voltage data were collected to ascertain the influence of each modification upon the back electron transfer (ET) dynamics of the DSCs. The primary effect of the additives alone or in tandem is to increase the open-circuit voltage. A second is to alter the short-circuit current density, J(SC). With dependence on the specifics of the system examined, any of a myriad of dynamics-related effects were observed to come into play, in both favorable (efficiency boosting) and unfavorable (efficiency damaging) ways. These effects include modulation of (a) charge-injection yields, (b) rates of interception of injected electrons by redox shuttles, and (c) rates of recombination of injected electrons with holes on surface-bound dyes. In turn, these influence charge-collection lengths, charge-collection yields, and onset potentials for undesired dark current. The microscopic origins of the effects appear to be related mainly to changes in driving force and/or electronic coupling for underlying component redox reactions. Perhaps surprisingly, only a minor role for modifier-induced shifts in conduction-band-edge energy was found. The combination of DSC-efficiency-relevant effects engendered by the modifiers was found to vary substantially as a function of the chemical identity of the redox shuttle employed. While types of modifiers are effective, a challenge going forward will be to construct systems in ways in which the benefits of organic and inorganic modifiers can be exploited in fully additive, or even synergistic, fashion.

Katz, Michael J.↗
DOE OSTI2020

Characteristics of Electron Precipitation During 40 Energetic Electron Injections Inferred via Subionospheric VLF Signal Propagation

Energetic electron injection events are associated with energetic electron precipitation (EEP) through possible resonant wave-particle interactions. Previous studies confirm the impacts of injection-driven precipitation on observed amplitude/phase of subionospheric VLF (very low frequency) signals transmitted from distant artificial transmitters. Currently, there are substantial uncertainties on precipitation characteristics and flux during injection events. In this work we study 40 injection events selected by Van Allen Probes particle data to investigate the changes in amplitude and phase of VLF signals at ground receivers across Canada during particle injection events. We model the ionospheric effect of the EEP flux to find its impact on VLF propagation and characterize the injection events. Typically, we find a clear phase advance of ~40° in the received VLF signal at Fort Smith (Canada, L = 8) transmitted from U.S. Navy communication transmitter NAA at Maine (USA). Comparing to other VLF transmitter-receiver paths in North America leads us to conclude that effects are only seen on paths with adequately large range >>200 km) through L > 7. Modeling the VLF phase change indicates that in the majority of events (>90%), less than 10% of the strong scattering limit inferred from particle flux measurements at the Van Allen Probes is required to obtain the observed VLF phase signature. The median precipitating flux during energetic particle injections is less than 4 × 10 6 el/cm 2 s sr (<10% of the strong scattering rate) for electrons above ~40 keV extracted from trapped particles energy spectrum. This implies that strong scattering is not typical for these 40 selected energetic electron injection events.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Estimating Electron Temperature and Density Using Van Allen Probe Data: Typical Behavior of Energetic Electrons in the Inner Magnetosphere

Abstract The Earth's inner magnetosphere contains multiple electron populations influenced by different factors. The cold electrons of the plasmasphere, warm plasma that contributes to the ring current, and the relativistic plasma of the radiation belts often seem to behave independently. Using omni‐directional flux and energy measurements from the HOPE and Magnetic Electron Ion Spectrometer instruments aboard the Van Allen Probes, we provide a detailed density and temperature description of the inner magnetosphere, offering a comprehensive statistical analysis of the entire Van Allen Probe era. While number density and temperature data at geosynchronous orbit are available, this study focuses on the warm plasma in the inner magnetosphere . Values of density and temperature are extracted by fitting energy and phase space density to obtain the distribution function. The fitted distributions are related to the zeroth and second moments to estimate the number density and temperature. Analysis has indicated that a two Maxwellian fit is sufficient over a wide range of and that there are two independent plasma populations. The more energetic population has a median number density of approximately and a temperature of around 130 keV, with a temperature peak observed between L * = 4 and L * = 4.5. This population is relatively uniform in magnetic local time (MLT). In contrast, the less energetic warm electron population has a median number density of about and a temperature of 7.4 keV. Strong statistical trends in density and temperature across both L * and MLT are presented, along with potential sources driving these variations.

58 GEOSCIENCES↗
DOE OSTI2021

Manipulating electron redistribution to achieve electronic pyroelectricity in molecular [FeCo] crystals

Pyroelectricity plays a crucial role in modern sensors and energy conversion devices. However, obtaining materials with large and nearly constant pyroelectric coefficients over a wide temperature range for practical uses remains a formidable challenge. Attempting to discover a solution to this obstacle, we combined molecular design of labile electronic structure with the crystal engineering of the molecular orientation in lattice. This combination results in electronic pyroelectricity of purely molecular origin. Here, we report a polar crystal of an [FeCo] dinuclear complex exhibiting a peculiar pyroelectric behavior (a substantial sharp pyroelectric current peak and an unusual continuous pyroelectric current at higher temperatures) which is caused by a combination of Fe spin crossover (SCO) and electron transfer between the high-spin Fe ion and redox-active ligand, namely valence tautomerism (VT). As a result, temperature dependence of the pyroelectric behavior reported here is opposite from conventional ferroelectrics and originates from a transition between three distinct electronic structures. The obtained pyroelectric coefficient is comparable to that of polyvinylidene difluoride at room temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Searching for promising new perovskite-based photovoltaic absorbers: the importance of electronic dimensionality

Searching for promising nontoxic and air-stable perovskite absorbers for solar cell applications has drawn extensive attention. Here, we show that a promising perovskite absorber should exhibit a high electronic dimensionality. Semiconductors that exhibit a high structural dimensionality, but a low electronic dimensionality have less promise as an absorber, because of barriers to isotropic current flow, enhanced electron/hole effective masses and fundamentally deeper defect states (more effective at causing recombination). Our concept accounts for the device performance of the perovskite-based solar cells reported in literature so far.

Xiao, Zewen↗