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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 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Beyond n-dopants for organic semiconductors: use of bibenzo[ d ]imidazoles in UV-promoted dehalogenation reactions of organic halides

2,2’-Bis(4-dimethylaminophenyl)- and 2,2'-dicyclohexyl-1,1',3,3'-tetramethyl-2,2',3,3'-tetrahydro-2,2'-bibenzo[ d ]imidazole ((N-DMBI) 2 and (Cyc-DMBI) 2 ) are quite strong reductants with effective potentials of ca. −2 V vs ferrocenium/ferrocene, yet are relatively stable to air due to the coupling of redox and bond-breaking processes. Here, we examine their use in accomplishing electron transfer-induced bond-cleavage reactions, specifically dehalogenations. The dimers reduce halides that have reduction potentials less cathodic than ca. −2 V vs ferrocenium/ferrocene, especially under UV photoexcitation (using a 365 nm LED). In the case of benzyl halides, the products are bibenzyl derivatives, whereas aryl halides are reduced to the corresponding arenes. The potentials of the halides that can be reduced in this way, quantum-chemical calculations, and steady-state and transient absorption spectroscopy suggest that UV irradiation accelerates the reactions via cleavage of the dimers to the corresponding radical monomers.

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

Hot-Carrier Photoluminescence in Low-Temperature CsSnI3 Nanocrystals

In the halide perovskites, the B-site metal lone-pairs electrons are strongly suspected to underpin many of the interesting properties of the inorganic halide perovskites. Recently, a stable low-temperature monoclinic polar phase was predicted for CsSnI3, opening the possibility of direct investigation of both these lone pair electrons and a ferroelectric distorted structure. To date there are no other reports of such a structure in CsSnI3, and a known low-temperature monoclinic structure in CsSnBr3 remains unexplored. We have found optical evidence of a transformation occurring around 240 K in CsSnI3 nanocrystals, with several changes in optical behavior below this transition point, including novel high-energy photoluminescene and new states in the transient absorption spectrum. We have successfully characterized the optical properties of this low-temperature phase and found evidence for a polar, monoclinic structure. Discovery of a stable monoclinic polar structure in the halide perovskites opens many new potential directions for further research and electronics applications.

14 SOLAR ENERGY↗
NASA NTRS1983

Pulse radiolysis of epoxy-based matrix materials

Electron beam pulse radiolysis (600 KeV, 3 nsec) experiments have been carried out on epoxy-based matrix materials. Time and wavelength resolved emission and transient absorption techniques as well as ESR studies have been utilized to identify and monitor short lived reactive intermediates resulting from energetic electron impact. An energy deactivation model based on the results of this work has been developed. Recombination of primary charged species is found to be fast, resulting in the formation of longer lived excited electronic states and radicals which control the subsequent energy deactivation.

Coulter, D. R.↗
NASA NTRS1989

Fast spectroscopic variations on rapidly-rotating, cool dwarfs. 3: Masses of circumstellar absorbing clouds on AB Doradus

New time-resolved H alpha, Ca II H and K and Mg II h and k spectra of the rapidly-rotating K0 dwarf star AB Doradus (= HD 36705). The transient absorption features seen in the H alpha line are also present in the Ca II and Mg II resonance lines. New techniques are developed for measuring the average strength of the line absorption along lines of sight intersecting the cloud. These techniques also give a measure of the projected cloud area. The strength of the resonance line absorption provides useful new constraints on the column densities, projected surface areas, temperatures and internal turbulent velocity dispersions of the circumstellar clouds producing the absorption features. At any given time the star appears to be surrounded by at least 6 to 10 clouds with masses in the range 2 to 6 x 10(exp 17) g. The clouds appear to have turbulent internal velocity dispersions of order 3 to 20 km/s, comparable with the random velocities of discrete filamentary structures in solar quiescent prominences. Night-to-night changes in the amount of Ca II resonance line absorption can be explained by changes in the amplitude of turbulent motions in the clouds. The corresponding changes in the total energy of the internal motions are of order 10(exp 29) erg per cloud. Changes of this magnitude could easily be activated by the frequent energetic (approximately 10(exp 34) erg) x ray flares seen on this star.

Cameron, A. Collier↗
NASA NTRS1990

Photophysical behavior of doubly bridged d7-d7 metal-metal bonded compounds - The crystal structure and the excited- and ground-state electronic spectra of Re2(CO)6(dmpm)2 (dmpm = bis/dimethylphosphino/ methane)

Re2(CO)6(dmpm)2 shows photophysical behavior in a rigid medium that differs dramatically from that observed in fluid solution. In a hydrocarbon glass at 77 K, metal-metal bond homolysis is suppressed and an intense phosphorescence is observed. The transient absorption spectrum, which shows only weak transitions to the red of the ground state 1(sigma-sigma asterisk) transition, permits assignment of the emitting state to a 3(sigma-sigma asterisk) transition. The crystal structure of Re2(CO)6(dmpm)2 is also reported. The ground-state electronic structure is discussed relative to the structural data.

Milder, Steven J.↗
NASA NTRS2000

Production of Star-Grazing and Star-Impacting Planetestimals via Orbital Migration of Extrasolar Planets

During the orbital migration of a giant extrasolar planet via ejection of planetesimals (as studied by Murray et al. in 1998), inner mean-motion resonances can be strong enough to cause planetesimals to graze or impact the star. We integrate numerically the motions of particles which pass through the 3:1 or 4:1 mean-motion resonances of a migrating Jupiter-mass planet. We find that many particles can be trapped in the 3:1 or 4:1 resonances and pumped to high enough eccentricities that they impact the star. This implies that for a planet migrating a substantial fraction of its semimajor axis, a fraction of its mass in planetesimals could impact the star. This process may be capable of enriching the metallicity of the star at a time when the star is no longer fully convective. Upon close approaches to the star, the surfaces of these planetesimals will be sublimated. Orbital migration should cause continuing production of evaporating bodies, suggesting that this process should be detectable with searches for transient absorption lines in young stars. The remainder of the particles will not impact the star but can be ejected subsequently by the planet as it migrates further inward. This allows the planet to migrate a substantial fraction of its initial semimajor axis by ejecting planetesimals.

Quillen, A. C.↗
DOE OSTI2021

Interlayer Triplet Energy Transfer in Dion-Jacobson 2D Perovskites Containing Naphthalene Diammonium Cations

The ability to tune the heterojunction energy level alignment in layered 2D perovskites is well documented, with both early works and more recent studies reporting interfacial triplet energy transfer in certain pairings of lead halide with small conjugated organic spacer cations. Such 2D perovskites are promising systems for sensitized molecular phosphorescence, which has varied applications in optoelectronics, solar energy conversion, and more. However, even for a given organic cation core, variations in the cation structure (e.g. location of the ammonium substituent, length of the alkyl linker, and valency of the cation) can dramatically alter the organic layer morphology and electronic coupling between the inorganic and organic layers. While interlayer triplet energy transfer has been studied in Ruddlesden-Popper 2D perovskites containing monovalent naphthalene cations, the photophysical properties of their Dion-Jacobson analogue, formed using divalent naphthalene cations, have not been reported. In this study, we examine interlayer energy transfer in a series of mixed-halide 2D perovskites formed by divalent naphthalene cations. We find that the sensitized phosphorescence in these compounds is dominated by naphthalene triplet excimer emission, but when the lead halide exciton level is tuned near resonance with the triplet level of naphthalene, emission from the naphthalene triplet monomer competes with triplet excimer formation. Interlayer energy transfer in these compounds is further supported by ultrafast transient absorption spectroscopy. Ultimately, the ability to gain control over interlayer interactions in layered 2D perovskites through cation design will help uncover new functions and applications for these materials.

2D↗
DOE OSTI2025

Solvated Electrons Have Multiple Personalities in Molten Salts

P-Crosscut: Solvated Electrons Have Multiple Personalities in Molten Salts [EFRC – MSEE] Alejandro Ramos-Ballesteros;1 Hung H. Nguyen;2 Kazuhiro Iwamatsu;3 Santanu Roy;4 Vyacheslav Bryantsev;4 Michael E. Woods;1 Ruchi Gakhar;1 Phillip Halstenberg;4 Bobby Layne;5 Jay A. LaVerne;6 Claudio J. Margulis:2* and James F. Wishart5* 1Idaho National Laboratory; 2The University of Iowa; 3Hunter College; 4Oak Ridge National Laboratory; 5Brookhaven National Laboratory; 6University of Notre Dame Abstract: The solvated (eS–) is a powerful reducing agent and one of the primary products of molten salt radiolysis. In these extreme high-temperature environments, the eS– can initiate cascades of redox processes that significantly alter the physical and chemical properties of a molten salt, posing challenges for molten salt reactor (MSR) performance and longevity. Consequently, mastering the fundamental behavior of the eS– could enable the design of specific molten salt mixtures with tailored Lewis acidities for controlling the speciation and chemical reactivity of the eS–, thereby mitigating its overall impact on MSR technologies. Here, we use time-resolved electron pulse radiolysis techniques for determining chemical kinetics and transient absorption spectra, combined with ab initio molecular dynamics simulations to explore the influence of multivalent metal cations on the fundamental speciation and distribution of eS– coordination environments.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗
DOE OSTI2026

Impact of Nd ions on the chemical kinetic behavior of radiolytic transients in molten LiCl-KCl-NdCl3 salt mixtures

Pyrochemical reprocessing technologies can be used to recover valuable materials from used nuclear fuel (UNF), such as uranium. However, other critical materials, such as fission product neodymium, are challenging to recover from molten chloride eutectic mixtures (LiCl-KCl) due to the presence of multivalent states (Nd2+/Nd3+), disproportionation reactions, and re-dissolution in the molten chloride salt. Understanding, predicting, and controlling these processes is further complicated by the presence of ionizing radiation fields, for which little is known on the interaction of neodymium ions with the radiolytic transients (es– and Cl2.–) in molten LiCl-KCl salt mixtures. Here, chemical kinetics, from integrated electron pulse irradiation and transient absorption spectroscopy, are presented for the reaction of Nd3+ ions with es– and Cl2.– as a function of temperature (400–600 ?).

36 - MATERIALS SCIENCE↗
DOE OSTI2023

Synchrotron based transient x-ray absorption spectroscopy for emerging solid-state energy materials

The rational design of cutting-edge materials for an efficient solar energy conversion process is a challenging task, which demands a fundamental understanding of the mechanisms operative during the photoinduced physical and chemical reactions. In response to these issues, progress in the field has steered attention toward the use of time-resolved spectroscopic techniques to resolve the multiple intermediate species involved in these photoinduced reactions. Thanks to the advent of pump–probe technique, which leads to the development of various time-resolved spectroscopic methods, significant progress has been made in understanding the photophysical and photochemical properties (e.g., excited state dynamics, charge transfer mechanism, charge separation dynamics, etc.) of energy materials. Synchrotron-based x-ray transient absorption (XTA) spectroscopy is one of the most important time-resolved techniques to unravel the direct correlation of the material structure with their photophysical properties owing to its unique capability in directly observing electronic and structural evolution simultaneously. As a result, the aim of this work is to provide a systematic overview of the recent progress in using XTA for capturing the structural dynamics associated with excited state and charge separation dynamics in emerging solid-state energy materials.

14 SOLAR ENERGY↗
NASA NTRS1994

Spectroscopic, orbital, and physical properties of the binary Feige 24 and detection of transient He II absorption in the system

We have obtained new high-dispersion optical spectroscopy at Kitt Peak National Observatory (KPNO) and new International Ultraviolet Explorer (IUE) spectroscopy of the white dwarf+red dwarf binary system Feige 24. The optical range shows a composite DA+dM spectrum, together with H I Balmer and He I emission. The orbital phase dependence of the emission shows that it results from extreme ultraviolet (EUV) light reprocessing in the red dwarf upper atmosphere. The systems close enough and hot enough to show this reprocessing signature only recently emerged from common-envelope evolution. The ultraviolet spectrum exclusively emanates from the white dwarf and shows numerous heavy element absorption lines. We measured accurate radial velocities of the red dwarf component motion, traced by both optical absorption and emission lines, and new radial velocities of the white dwarf, traced by ultraviolet Fe V lines. Combining these measurements, we refined the orbital parameters presented by Vennes et al. (1991), and we confirmed that the white dwarf gravitational redshift is exceptionally small with 9 +/- 2 km/s. From this we deduced that the interior is either pure helium or carbon with a thick hydrogen layer, and we derived, for the combined interior compositions, a white dwarf mass and radius of M(sub WD) = 0.44-050 solar mass and R(sub WD) = 0.028-0.036 solar radius. We suggest that Feige 24 could be a typical case of close binary evolution leading to the formation of a low-mass helium white dwarf. The mass of the red dwarf and the inclination of the system naturally follow: M(sub dM) = 0.26-0.33 solar mass, i greater than or equal to 75 deg. High-dispersion H-alpha line profiles are asymmetrical, strongly enhanced toward the blue, suggesting a moving atmosphere possibly linked to a mass loss rate of 10(exp -10) solar mass/yr. The IUE spectra taken when the system is near inferior conjunction show strong He II 1640 A absorption. The profile is highly variable in width and intensity. Because it is correlated with the passage of the white dwarf at inferior conjunction, the absorption may occur in some foreground plasma emanated by the red dwarf and accumulating near a Lagrangian point or, alternatively, it may originate in an accretion spot on the white dwarf surface coaligned with the major orbital axis. Either way, the He II detection may imply substantial mass loss from the red dwarf with a corollary reclassification of Feige 24 as a mixed He/H DAO white dwarf resulting from accretion of secondary mass-loss material. Feige 24 is the prototype of a class of young, EUV-emitting, binary systems comprising a late main sequence secondary and a hot H-rich white dwarf; the class is characterized by optical and ultraviolet photospheric He II absorption, circumstellar C IV lambda (1550) absorption, and by the presence of EUV-induced, phase-dependent Balmer fluorescence. These young systems present the best opportunity to constrain theory of common-envelope evolution.

Vennes, Stephane↗
NASA NTRS1986

Transient gain-versus-absorption laser probing of spin-orbit states, kinetics and dynamics

The spin-orbit populations of excited (2P1/2) and ground (2P3/2) state Br atoms at 2714 nm and I atoms at 1315 nm are examined using a tunable F-center laser and a diode laser. The transient laser gain-versus-absorption measurements are utilized to estimate quantum yields of the spin-orbit states in the photodissociation of Br- and I-containing compounds; the continuum yields for Br2 are investigated in terms of temperature. The collisional release, Doppler velocity effects, and differing reactivity of the spin-orbit excited and ground state atoms are studied. It is noted that the transient gain versus absorption technique is applicable to the analysis of kinetic phenomena due to its high sensitivity and excellent time resolution.

Smedley, John E.↗
DOE OSTI2022

Janus Monolayers for Ultrafast and Directional Charge Transfer in Transition Metal Dichalcogenide Heterostructures

Charge transfer properties of van der Waals heterostructures formed by Janus and regular transition metal dichalcogenide monolayers are studied by time-resolved pump–probe measurements and photoluminescence spectroscopy. Measurements of electron and hole transfer in three heterostructures with atomic layer sequences of S–W–Se/S–W–S, Se–W–S/S–W–S, and S–W–Se/Se–W–Se reveal that charge transfer from regular to Janus monolayers is ultrafast regardless of the direction of the built-in electric field of the Janus monolayer (Janus field). However, the charge transfer from Janus to regular layers is directional and controlled by the Janus field. When the current direction is along the field, the charge transfer is ultrafast and efficient, while the field blocks the charge transfer with an opposite charge current direction. The transferred carriers form interlayer excitons with extended lifetimes compared to the intralayer excitons. The demonstrated ultrafast and directional charge transfer between Janus and regular TMD layers shows that the Janus structures can be used to make 2D heterostructures with efficient and directional charge transfer properties.

36 MATERIALS SCIENCE↗