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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 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Characterising local environments in high energy density Li-ion battery cathodes: a combined NMR and first principles study of LiFe x Co 1-x PO 4

Olivine-type LiCoPO4 (LCP) is a high energy density lithium ion battery cathode material due to the high voltage of the Co2+/Co3+ redox reaction. However, it displays a significantly poorer electrochemical performance than its more widely investigated isostructural analogue LiFePO4 (LFP). The co-substituted LiFexCo1-xPO4 olivines combine many of the positive attributes of each end member compound and are promising next-generation cathode materials. Here, the fully lithiated x = 0, 0.25, 0.5, 0.75 and 1 samples are extensively studied using 31P solid-state nuclear magnetic resonance (NMR). Practical approaches to broadband excitation and for the resolution of the isotropic resonances are described. First principles hybrid density functional calculations are performed on the Fermi contact shift (FCS) contributions of individual M–O–P pathways in the end members LFP and LCP and compared with the fitted values extracted from the LiFexCo1-xPO4 experimental data. Combining both data sets, the FCS for the range of local P environments expected in LiFexCo1-xPO4 have been calculated and used to assign the NMR spectra. Due to the additional unpaired electron in d6 Fe2+ as compared with d7 Co2+ (both high spin), LFP is expected to have larger Fermi contact shifts than LCP. However, two of the Co–O–P pathways in LCP give rise to noticeably larger shifts and the unexpected appearance of peaks outside the range delimited by the pure LFP and LCP 31P shifts. This behaviour contrasts with that observed previously in LiFexMn1-xPO4, where all 31P shifts lay within the LiMnPO4–LFP range. Although there are 24 distinct local P environments in LiFexCo1-xPO4, these group into seven resonances in the NMR spectra, due to significant overlap of the isotropic shifts. The local environments that give rise to the largest contributions to the spectral intensity are identified and used to simplify the assignment. This provides a tool for future studies of the electrochemically-cycled samples, which would otherwise be challenging to interpret.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Aggregation of cyclic polypeptoids bearing zwitterionic end-groups with attractive dipole–dipole and solvophobic interactions: a study by small-angle neutron scattering and molecular dynamics simulation

Aggregation behavior of cyclic polypeptoids bearing zwitterionic end-groups in methanol has been studied using a combination of experimental and simulation techniques. Here, the data from SANS and cryo-TEM indicate that the solution contains small clusters of these cyclic polypeptoids, ranging from a single polypeptoid chain to small oligomers, while the linear counterpart shows no cluster formation. Atomistic molecular dynamics simulations reveal that the driving force for this clustering behavior is due to the interplay between the effective repulsion due to the solvation of the dipoles formed by the charged end-groups in each polypeptoid chain and the attractive forces due to dipole–dipole interactions and the solvophobic effect.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

A fluorescence-electrochemical study of carbon nanodots (CNDs) in bio- and photoelectronic applications and energy gap investigation

Carbon nanodots (CNDs) have attracted significant attention due to their superior solubility, biocompatibility, tunable photoluminescence, and opto-electronic properties. Our work describes a new fluorescence-based spectroelectrochemistry approach to simultaneously study the photoluminescence and wavelength dependent photocurrent of microwave synthesized CNDs. The fluorescence of CNDs shows selective quenching upon a reversible redox couple, ferricyanide/ferrocyanide, reaction during cyclic voltammetry. The CND modified gold slide electrode demonstrates wavelength dependent photocurrent generation during the fluorescence-electrochemical study, suggesting the potential application of CNDs in photoelectronics. UV-Vis absorption and electrochemistry are used to quantify the energy gap of the CNDs, and then to calibrate a Hückel model for CNDs’ electronic energy levels. The Hückel (or tight binding) model treatment of an individual CND as a molecule combines the conjugated π states (C[double bond, length as m-dash]C) with the functional groups (C[double bond, length as m-dash]O, C–O, and COOH) associated with the surface electronic states. This experimental and theoretical investigation of CNDs provides a new perspective on the optoelectronic properties of CNDs and should aid in their development for practical use in biomedicine, chemical sensing, and photoelectric devices.

36 MATERIALS SCIENCE↗
DOE OSTI2018

A combined crossed molecular beams and computational study on the formation of distinct resonantly stabilized C 5 H 3 radicals via chemically activated C 5 H 4 and C 6 H 6 intermediates

The crossed molecular beams technique was utilized to investigate the formation of three isomers of resonantly stabilized (C 5 H 3 ) radicals along with their d 2 -substituted counterparts via the bimolecular reactions of singlet/triplet dicarbon [C 2 (X 1 Σ + g /a 3 Π u )] with methylacetylene [CH 3 CCH(X 1 A 1 )], d 3 -methylacetylene [CD 3 CCH(X 1 A 1 )], and 1-butyne [C 2 H 5 CCH(X 1 A')] at collision energies up to 26 kJ mol -1 via chemically activated singlet/triplet C 5 H 4 /C 5 D 3 H and C 6 H 6 intermediates. These studies exploit a newly developed supersonic dicarbon [C 2 (X 1 Σ + g /a 3 Π u )] beam generated via photolysis of tetrachloroethylene [C 2 Cl 4 (X 1 A g )] by excluding interference from carbon atoms, which represent the dominating (interfering) species in ablation-based dicarbon sources. We assessed the performance of the dicarbon [C 2 (X 1 Σ + g /a 3 Π u )] beam in reactions with methylacetylene [CH 3 CCH(X 1 A 1 )] and d 3 -methylacetylene [CD 3 CCH(X 1 A 1 )]; the investigations demonstrate that the reaction dynamics match previous studies in our laboratory utilizing ablation-based dicarbon sources involving the synthesis of 1,4-pentadiynyl-3 [HCCCHCCH(X 2 B 1 )] and 2,4-pentadiynyl-1 [H 2 CCCCCH(X 2 B 1 )] radicals via hydrogen (deuterium) atom elimination. Considering the C 2 (X 1 Σ + g /a 3 Π u )–1-butyne [C 2 H 5 CCH(X 1 A')] reaction, the hitherto elusive methyl-loss pathway was detected. This channel forms the previously unknown resonantly stabilized penta-1-yn-3,4-dienyl-1 [H 2 CCCHCC(X 2 A)] radical along with the methyl radical [CH 3 (X 2 A 2 ")] and is open exclusively on the triplet surface with an overall reaction energy of -86 ± 10 kJ mol -1 . The preferred reaction pathways proceed first by barrierless addition of triplet dicarbon to the π-electronic system of 1-butyne, either to both acetylenic carbon atoms or to the sterically more accessible carbon atom, to form the methyl-bearing triplet C 6 H 6 intermediates [ i4 1b ] and [ i8 1b ], respectively, with the latter decomposing via a tight exit transition state to penta-1-yn-3,4-dienyl-1 [(H 2 CCCHCC(X 2 A)] plus the methyl radical [CH 3 (X 2 A 2 ")]. The successful unraveling of this methyl-loss channel – through collaborative experimental and computational efforts – underscores the viability of the photolytically generated dicarbon beam as an unprecedented tool to access reaction dynamics underlying the formation of resonantly stabilized free radicals (RSFR) that are vital to molecular mass growth processes that ultimately lead to polycyclic aromatic hydrocarbons (PAHs)

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

Two-dimensional electronic-vibrational spectroscopic study of conical intersection dynamics: an experimental and electronic structure study

The relaxation from the lowest singlet excited state of the triphenylmethane dyes, crystal violet and malachite green, is studied via two-dimensional electronic-vibrational (2DEV) spectroscopy. After excitation of the dyes at their respective absorption maxima, the ensuing excited state dynamics are tracked by monitoring the C[double bond, length as m-dash]C aromatic stretch. With the aid of electronic structure calculations, the observed transitions in the 2DEV spectra are assigned to specific geometries and a detailed story of the evolution of the nuclear wavepacket as it diffuses on the excited state potential energy surface (PES) and ultimately passes through the conical intersection is developed. Notably, it is revealed that the relaxation of the lowest singlet excited state involves intramolecular charge transfer while the nuclear wavepacket is on the excited state PES. Finally, through analyzing the center line slopes of the measured peaks, we show how both solvent motions and changes in the molecular dipole moment affect the correlation between electronic and vibrational degrees of freedom. This work clearly demonstrates the usefulness of 2DEV spectroscopy in following the motion of nuclear wavepackets after photoexcitation and in studying the interactions between the molecular dipole moment and surrounding solvent environment.

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

Enhancing Electrocatalysis for Hydrogen Production over CoP Catalyst by Strain: A Density Functional Theory Study

The facet-dependent strain effects on the hydrogen evolution reaction catalyzed by CoP were studied using density functional theory methods. We show that both atomic and electronic effects need to be taken into consideration to understand the strain effects. For the (111) surface, tensile strain promotes hydrogen evolution at all the levels of hydrogen coverage. For the (101) surface, a moderate tensile strain of ~3% endows this facet with optimum performance.

Liu, Fanghan↗
DOE OSTI2021

Nickel(ii) complexes based on dithiolate–polyamine binary ligand systems: crystal structures, hirshfeld surface analysis, theoretical study, and catalytic activity study on photocatalytic hydrogen generation

To ascertain the influence of binary ligand systems [1,1-dicyanoethylene-2,2-dithiolate (i-mnt -2 ) and polyamine {tetraen = tris(2-aminoethyl)amine, tren = diethylene triamine and opda = o-phenylenediamine}] on the coordination modes of the Ni(II) metal center and resulting supramolecular architectures, a series of nickel(II) thiolate complexes [Ni(tetraen)(i-mnt)](DMSO) (1), [Ni 2 (tren) 2 (i-mnt) 2 ] (2), and [Ni 2 (i-mnt) 2 (opda) 2 ] n (3) have been synthesized in high yield in one step in water and structurally characterized by single crystal X-ray crystallography and spectroscopic techniques. X-ray diffraction studies disclose the diverse i-mnt -2 coordination to the Ni +2 center in the presence of active polyamine ligands, forming a slightly distorted octahedral geometry (NiN 4 S 2 ) in 1, square planar (NiS 4 ) and distorted octahedral geometries (NiN 6 ) in the bimetallic co-crystallized aggregate of cationic [Ni(tren) 2 ] +2 and anionic [Ni(i-mnt) 2 ] -2 in 2, and a one dimensional (1D) polymeric chain along the [100] axis in 3, having consecutive square planar (NiS 4 ) and octahedral (NiN 6 ) coordination kernels. The N–H···O, N–H···S, N–H···N, N–H···S, N–H···N, and N–H···O type hydrogen bonds stabilize the supramolecular assemblies in 1, 2, and 3 respectively imparting interesting graph-set-motifs. The molecular Hirshfeld surface analyses (HS) and 2D fingerprint plots were utilized for decoding all types of non-covalent contacts in the crystal networks. Atomic HS analysis of the Ni +2 centers reveals significant Ni–N metal–ligand interactions compared to Ni–S interactions. We have also studied the unorthodox interactions observed in the solid state structures of 1–3 by QTAIM and NBO analyses. Moreover, all the complexes proved to be highly active water reduction co-catalysts (WRC) in a photo-catalytic hydrogen evolution process involving iridium photosensitizers, wherein 2 and 3 having a square planar arrangement around the nickel center(s) – were found to be the most active ones, achieving 1000 and 1119 turnover numbers (TON), respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Study of the one-way speed of light anisotropy with particle beams

Concepts of high precision studies of the one-way speed of light anisotropy are discussed. The high energy particle beam allows measurement of a one-way speed of light anisotropy (SOLA) via analysis of the beam momentum variation with sidereal phase without the use of synchronized clocks. High precision beam position monitors could provide accurate monitoring of the beam orbit and determination of the particle beam momentum with relative accuracy on the level of 10^-10, which corresponds to a limit on SOLA of 10^-18 with existing storage rings. A few additional versions of the experiment are also presented.

Wojtsekhowski, Bogdan B.↗
DOE OSTI2013

Defects in paramagnetic Co-doped ZnO films studied by transmission electron microscopy

We study planar defects in epitaxial Co:ZnO dilute magnetic semiconductor thin films deposited on c-plane sapphire (Al{sub 2}O{sub 3}), as well as the Co:ZnO/Al{sub 2}O{sub 3} interface, using aberration-corrected transmission electron microscopy and electron energy-loss spectroscopy. Co:ZnO samples that were deposited using pulsed laser deposition and reactive magnetron sputtering are both found to contain extrinsic stacking faults, incoherent interface structures, and compositional variations within the first 3–4 Co:ZnO layers next to the Al{sub 2}O{sub 3} substrate. The stacking fault density is in the range of 10{sup 17} cm{sup −3}. We also measure the local lattice distortions around the stacking faults. It is shown that despite the relatively high density of planar defects, lattice distortions, and small compositional variation, the Co:ZnO films retain paramagnetic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways

Solid-liquid interfaces are at the heart of many modern-day technologies and provide a challenge to many materials simulation methods. A realistic first-principles computational study of such systems entails the inclusion of solvent effects. In this work, we implement an implicit solvation model that has a firm theoretical foundation into the widely used density-functional code Vienna ab initio Software Package. The implicit solvation model follows the framework of joint density functional theory. We describe the framework, our algorithm and implementation, and benchmarks for small molecular systems. We apply the solvation model to study the surface energies of different facets of semiconducting and metallic nanocrystals and the S N 2 reaction pathway. We find that solvation reduces the surface energies of the nanocrystals, especially for the semiconducting ones and increases the energy barrier of the S N 2 reaction.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Cohesion energetics of carbon allotropes: Quantum Monte Carlo study

We have performed quantum Monte Carlo calculations to study the cohesion energetics of carbon allotropes, including sp{sup 3}-bonded diamond, sp{sup 2}-bonded graphene, sp–sp{sup 2} hybridized graphynes, and sp-bonded carbyne. The computed cohesive energies of diamond and graphene are found to be in excellent agreement with the corresponding values determined experimentally for diamond and graphite, respectively, when the zero-point energies, along with the interlayer binding in the case of graphite, are included. We have also found that the cohesive energy of graphyne decreases systematically as the ratio of sp-bonded carbon atoms increases. The cohesive energy of γ-graphyne, the most energetically stable graphyne, turns out to be 6.766(6) eV/atom, which is smaller than that of graphene by 0.698(12) eV/atom. Experimental difficulty in synthesizing graphynes could be explained by their significantly smaller cohesive energies. Finally, we conclude that the cohesive energy of a newly proposed graphyne can be accurately estimated with the carbon–carbon bond energies determined from the cohesive energies of graphene and three different graphynes considered here.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Atomistic simulation study of short pulse laser interactions with a metal target under conditions of spatial confinement by a transparent overlayer

The distinct characteristics of short pulse laser interactions with a metal target under conditions of spatial confinement by a solid transparent overlayer are investigated in a series of atomistic simulations. The simulations are performed with a computational model combining classical molecular dynamics (MD) technique with a continuum description of the laser excitation, electron-phonon equilibration, and electronic heat transfer based on two-temperature model (TTM). Two methods for incorporation of the description of a transparent overlayer into the TTM-MD model are designed and parameterized for Ag-silica system. The material response to the laser energy deposition is studied for a range of laser fluences that, in the absence of the transparent overlayer, covers the regimes of melting and resolidification, photomechanical spallation, and phase explosion of the overheated surface region. In contrast to the irradiation in vacuum, the spatial confinement by the overlayer facilitates generation of sustained high-temperature and high-pressure conditions near the metal-overlayer interface, suppresses the generation of unloading tensile wave, decreases the maximum depth of melting, and prevents the spallation and explosive disintegration of the surface region of the metal target. At high laser fluences, when the laser excitation brings the surface region of the metal target to supercritical conditions, the confinement prevents the expansion and phase decomposition characteristic for the vacuum conditions leading to a gradual cooling of the hot compressed supercritical fluid down to the liquid phase and eventual solidification. The target modification in this case is limited to the generation of crystal defects and the detachment of the metal target from the overlayer.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Physical origins of weak H{sub 2} binding on carbon nanostructures: Insight from ab initio studies of chemically functionalized graphene nanoribbons

We have performed ab initio density functional theory calculations, incorporating London dispersion corrections, to study the absorption of molecular hydrogen on zigzag graphene nanoribbons whose edges have been functionalized by OH, NH{sub 2}, COOH, NO{sub 2}, or H{sub 2}PO{sub 3}. We find that hydrogen molecules always preferentially bind at or near the functionalized edge, and display induced dipole moments. Binding is generally enhanced by the presence of polar functional groups. The largest gains are observed for groups with oxygen lone pairs that can facilitate local charge reorganization, with the biggest single enhancement in adsorption energy found for “strong functionalization” by H{sub 2}PO{sub 3} (115 meV/H{sub 2} versus 52 meV/H{sub 2} on bare graphene). We show that for binding on the “outer edge” near the functional group, the presence of the group can introduce appreciable contributions from Debye interactions and higher-order multipole electrostatic terms, in addition to the dominant London dispersion interactions. For those functional groups that contain the OH moiety, the adsorption energy is linearly proportional to the number of lone pairs on oxygen atoms. Mixed functionalization with two different functional groups on a graphene edge can also have a synergistic effect, particularly when electron-donating and electron-withdrawing groups are combined. For binding on the “inner edge” somewhat farther from the functional group, most of the binding again arises from London interactions; however, there is also significant charge redistribution in the π manifold, which directly reflects the electron donating or withdrawing capacity of the functional group. Our results offer insight into the specific origins of weak binding of gas molecules on graphene, and suggest that edge functionalization could perhaps be used in combination with other strategies to increase the uptake of hydrogen in graphene. They also have relevance for the storage of hydrogen in porous carbon materials, such as activated carbons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

An ITPA joint experiment to study runaway electron generation and suppression

Recent results from an ITPA joint experiment to study the onset, growth, and decay of relativistic electrons (REs) indicate that loss mechanisms other than collisional damping may play a dominant role in the dynamics of the RE population, even during the quiescent I{sub p} flattop. Understanding the physics of RE growth and mitigation is motivated by the theoretical prediction that disruptions of full-current (15 MA) ITER discharges could generate up to 10 MA of REs with 10–20 MeV energies. The ITPA MHD group is conducting a joint experiment to measure the RE detection threshold conditions on a number of tokamaks under quasi-steady-state conditions in which V{sub loop}, n{sub e}, and REs can be well-diagnosed and compared to collisional theory. Data from DIII-D, C-Mod, FTU, KSTAR, and TEXTOR have been obtained so far, and the consensus to date is that the threshold E-field is significantly higher than predicted by relativistic collisional theory, or conversely, the density required to damp REs is significantly less than predicted, which could have significant implications for RE mitigation on ITER.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

Development of the CD Symcap platform to study gas-shell mix in implosions at the National Ignition Facility

Surrogate implosions play an important role at the National Ignition Facility (NIF) for isolating aspects of the complex physical processes associated with fully integrated ignition experiments. The newly developed CD Symcap platform has been designed to study gas-shell mix in indirectly driven, pure T{sub 2}-gas filled CH-shell implosions equipped with 4 μm thick CD layers. This configuration provides a direct nuclear signature of mix as the DT yield (above a characterized D contamination background) is produced by D from the CD layer in the shell, mixing into the T-gas core. The CD layer can be placed at different locations within the CH shell to probe the depth and extent of mix. CD layers placed flush with the gas-shell interface and recessed up to 8 μm have shown that most of the mix occurs at the inner-shell surface. In addition, time-gated x-ray images of the hotspot show large brightly radiating objects traversing through the hotspot around bang-time, which are likely chunks of CH/CD plastic. This platform is a powerful new capability at the NIF for understanding mix, one of the key performance issues for ignition experiments.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗