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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,783 records · Page 99
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Direct Measurements of Carrier Transport in Polycrystalline Methylammonium Lead Iodide Perovskite Films with Transient Grating Spectroscopy

Hybrid organic-inorganic halide perovskites have been proposed in many optoelectronic applications, but critical to their increasing functionality and utility is understanding and controlling carrier transport. Here, we use light-induced transient grating spectroscopy to probe directly carrier transport in polycrystalline methylammonium lead iodide perovskite thin films using a weakly perturbative and noncontact method. The data reveal intrinsic diffusion characteristics of the charge carriers in the material and agree well with a simulated model of charge transport in which grain boundaries act as barriers to carrier movement.

14 SOLAR ENERGY↗
DOE OSTI2018

Transient Kinetic Selectivity in Nanotubes Growth on Solid Co–W Catalyst

Solid Co–W catalysts have been shown to yield single-walled carbon nanotubes (CNT) with high selectivity, simplistically attributed to CNT-catalyst symmetry match for certain chiral indices (n,m). Here, based on large-scale first-principles calculations combined with kinetic Monte Carlo simulations, we show instead that such selectivity arises from a complex kinetics of growth. The solid Co7W6 catalyst strongly favors a restructured, asymmetric CNT edge which entails preferential nucleation of tubes with 2m < n but much faster growth of chiral tubes with n ≤ 2m. We uncover a tendency of interface defects formation that, although rare, drive CNT type change from smaller to larger chiral angles (zigzag to armchair). Furthermore, being both least prone to defects and fast growing, the (12,6) CNT appears as a transient, kinetics-selected type reaching highest abundance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Mechanism of CO 2 Hydrogenation on Pd/Al 2 O 3 Catalysts: Kinetics and Transient DRIFTS-MS Studies

The hydrogenation of CO 2 was investigated over a wide range of reaction conditions, using two Pd/γ-Al 2 O 3 catalysts with different Pd loadings (5% and 0.5%) and dispersions (~11% and ~100%, respectively). Turnover rates for CO and CH 4 formation were both higher over 5% Pd/Al 2 O 3 with a larger average Pd particle size than those over 0.5% Pd/Al 2 O 3 with a smaller average particle size. The selectivity to methane (22-40%) on 5% Pd/Al 2 O 3 was higher by a factor of 2-3 than that on 0.5% Pd/Al 2 O 3 . The drastically different rate expressions and apparent energies of activation for CO and CH 4 formation lead us to conclude that reverse water gas shift and CO 2 methanation do not share the same rate-limiting step on Pd, and that the two pathways are probably catalyzed at different surface sites. Measured reaction orders in CO 2 and H 2 pressures were similar over the two catalysts, suggesting that the reaction mechanism for each pathway does not change with particle size. In accordance, the DRIFTS results reveal that the prevalent surface species and their evolution patterns are comparable on the two catalysts during transient and steady-state experiments, switching feed gases among CO 2 , H 2 and CO 2 +H 2 . The DRIFTS and MS results also demonstrate that no direct dissociation of CO 2 takes place over the two catalysts, and that CO 2 has to first react with surface hydroxyls on the oxide support. The thus-formed bicarbonates react with dissociatively adsorbed hydrogen on Pd particles to produce adsorbed formate species (bifunctional catalyst: CO 2 activation on the oxide support, and H 2 dissociation on the metal particles). Formates near the Pd particles (most likely at the metal/oxide interface) can react rapidly with adsorbed H to produce CO, which then adsorbs on the metallic Pd particles. Two types of Pd sites are identified: one has a weak interaction with CO, which easily desorbs into gas phase at reaction temperatures, while the other interacts more strongly with CO, which is mainly in multi-bound forms and remains stable in He flow at high temperatures, but is reactive towards adsorbed H atoms on Pd leading eventually to CH 4 formation. 5% Pd/Al 2 O 3 contains a larger fraction of terrace sites favorable for forming these more stable CO species than 0.5% Pd/Al 2 O 3 . Consequently, we propose that the difference in the formation rate and selectivity to CH 4 on different Pd particle sizes stems from the different concentrations of the reactive intermediate for the methanation pathway on the Pd surface. JS gratefully acknowledges the financial support of this work by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Mechanocatalytic Ammonia Synthesis over TiN in Transient Microenvironments

Environmentally friendly and energy-efficient ways to produce ammonia are essential to meet global food demands. In this study, a new approach for ammonia production at nominally ambient conditions is introduced. As proof of concept, ammonia is synthesized mechanocatalytically by ball milling titanium in a continuous gas flow. The ammonia synthesis reaction is proposed to follow a transient Mars–van Krevelen mechanism under mechanically activated conditions, where molecular nitrogen incorporation into the titanium lattice and titanium nitride hydrogenation occur in thermodynamically distinct environments. X-ray powder diffraction and X-ray absorption spectroscopy confirm the formation of titanium nitride from titanium and N2. The reactivity of nitrided titanium supports that lattice nitrogen plays a role in ammonia formation. The in situ formed titanium nitride is catalytically active, and the nitride regeneration reaction is determined to be the rate-limiting step. A preliminary technoeconomic analysis shows that this approach could be feasible for distributed ammonia production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Large Transient Optical Modulation of Epsilon-Near-Zero Colloidal Nanocrystals

Here, epsilon-near-zero materials may be synthesized as colloidal nanocrystals which display large magnitude subpicosecond switching of infrared localized surface plasmon resonances. Such nanocrystals offer a solution-processable, scalable source of tunable metamaterials compatible with arbitrary substrates. Under intraband excitation, these nanocrystals display a red-shift of the plasmon feature arising from the low electron heat capacities and conduction band nonparabolicity of the oxide. Under interband pumping, they show in an ultrafast blueshift of the plasmon resonance due to transient increases in the carrier density. Combined with their high-quality factor, large changes in relative transmittance (+86%) and index of refraction (+85%) at modest control fluences (<5 mJ/cm 2 ) suggest that these materials offer great promise for all-optical switching, wavefront engineering, and beam steering operating at terahertz switching frequencies.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Transient Catenation in a Zirconium-Based Metal–Organic Framework and Its Effect on Mechanical Stability and Sorption Properties

Interpenetration of two or more sublattices is common among many metal–organic frameworks (MOFs). In this study, we study the evolution of one zirconium cluster-based, 3,8-connected MOF from its non-interpenetrated (NU-1200) to interpenetrated (STA-26) isomer. We observe this transient catenation process indirectly using ensemble methods, such as nitrogen porosimetry and X-ray diffraction, and directly, using high-resolution transmission electron microscopy. The approach detailed here will serve as a template for other researchers to monitor the interpenetration of their MOF samples at the bulk and single-particle limits. We investigate the mechanical stability of both lattices experimentally by pressurized in situ X-ray diffraction and nanoindentation as well as computationally with density functional theory calculations. Both lines of study reveal that STA-26 is considerably more mechanically stable than NU-1200. We conclude this study by demonstrating the potential of these MOFs and their mixed phases for the capture of gaseous n-hexane, used as a structural mimic for the chemical warfare agent sulfur mustard gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Mechanisms of the Cu(I)-Catalyzed Intermolecular Photocycloaddition Reaction Revealed by Optical and X-ray Transient Absorption Spectroscopies

The [2 + 2] photocycloaddition provides a simple, single-step route to cyclobutane moieties that would otherwise be disfavored or impossible due to ring strain and/or steric interactions. We have used a combination of optical and X-ray transient absorption spectroscopies to elucidate the mechanism of the Cu(I)-catalyzed intermolecular photocycloaddition reaction using norbornene and cyclohexene as model substrates. We find that for norbornene the reaction proceeds through an initial metal-to-ligand charge transfer (MLCT) state that persists for 18 ns before the metal returns to the monovalent oxidation state. The Cu K-edge spectrum continues to evolve until ~5 μs and then remains unchanged for the 50 μs duration of the measurement, reflecting product formation and ligand dissociation. We hypothesize that the MLCT transition and reverse electron transfer serve to sensitize the triplet excited state of one of the norbornene ligands, which then dimerizes with the other to give the product. For the case of cyclohexene, however, we do not observe a charge transfer state following photoexcitation and instead find evidence for an increase in the metal–ligand bond strength that persists for several ns before product formation occurs. This is consistent with a mechanism in which ligand photoisomerization is the initial step, which was first proposed by Salomon and Kochi in 1974 to explain the stereoselectivity of the reaction. Furthermore, our investigation reveals how this photocatalytic reaction may be directed along strikingly disparate trajectories by only very minor changes to the structure of the substrate.

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

Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles

We disclose a strategy for Ni-catalyzed regioselective dicarbofunctionalization of olefins in styrene derivatives by intercepting Heck C(sp 3 )-NiX intermediates with arylzinc reagents. This approach utilizes a readily removable imine as a coordinating group that plays a dual role of intercepting oxidative addition species derived from aryl halides and triflates to promote Heck carbometallation, and stabilizing the Heck C(sp 3 )-NiX intermediates as transient metallacycles to suppress β-hydride elimination and facilitate transmetalation/reductive elimination steps. This method affords diversely-substituted 1,1,2-riarylethyl products that occur as structural motifs in various natural products.

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

Ultrafast Intersystem Crossing in Acetylacetone via Femtosecond X-ray Transient Absorption at the Carbon K-Edge

Here, molecular triplet states constitute a crucial gateway in the photochemical reactions of organic molecules by serving as a reservoir for the excess electronic energy. Here, we report the remarkable sensitivity of soft X-ray transient absorption spectroscopy for following the intricate electronic structure changes accompanying the non-adiabatic transition of an excited molecule from the singlet to the triplet manifold. Core-level X-ray spectroscopy at the carbon-1s K-edge (284 eV) is applied to identify the role of the triplet state (T 1 , 3 ππ*) in the ultraviolet-induced photochemistry of pentane-2,4-dione (acetylacetone, AcAc). The excited-state dynamics initiated at 266 nm ( 1 ππ*, S 2 ) is investigated with element- and site-specificity using broadband soft X-ray pulses produced by high harmonic generation, in combination with time-dependent density functional theory calculations of the X-ray spectra for the excited electronic singlet and triplet states. The evolution of the core-to-valence resonances at the carbon K-edge establishes an ultrafast population of the T 1 state ( 3 ππ*) in AcAc via intersystem crossing on a 1.5 ± 0.2 ps time scale.

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

Probing the Impact of Solvation on Photoexcited Spin Crossover Complexes with High-Precision X-ray Transient Absorption Spectroscopy

Investigating the photoinduced electronic and structural response of bistable molecular building blocks incorporating transition metals in solution phase constitutes a necessary stepping stone for steering their properties towards applications and perfomance optimizations. Here, this paper presents a detailed X-ray transient absorption (XTA) spectroscopy study of a prototypical spin crossover (SCO) complex [Fe II (mbpy) 3 ] 2+ (where mbpy=4,4’-dimethyl-2,2’-bipyridine) with a [Fe II N 6 ] first coordination shell in water (H 2 O) and acetonitrile (CH 3 CN). The unprecedented data quality of the XTA spectra together with the direct fitting of the difference spectra in k space using a large number of scattering paths enables resolving the subtle difference in the photoexcited structures of an Fe II complex in two solvents for the first time. Also, compared to the low spin (LS) 1 A 1 state, the average Fe-N bond elongations for the photoinduced high spin (HS) 5 T 2 state are found to be 0.181 ± 0.003 Å in H 2 O and 0.199 ± 0.003 Å in CH 3 CN. This difference in structural response is attributed to ligand-solvent interactions that are stronger in H 2 O than in CH 3 CN for the HS excited state. Our studies demonstrate that, although the metal center of [Fe II (mbpy) 3 ] 2+ could have been expected to be rather shielded by the three bidentate ligands with quasi-octahedral-coordination, the ligand field strength in the HS excited state is nevertheless indirectly affected by solvation that modifies the charge distribution within the Fe-N covalent bonds. More generally, this work highlights the importance of including solvation effects in order to develop a generalized understanding of the spin-state switching at the atomic level.

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

Photoinduced Heterocyclic Ring Opening of Furfural: Distinct Open-Chain Product Identification by Ultrafast X-ray Transient Absorption Spectroscopy

The ultraviolet-induced photochemistry of five-membered heterocyclic rings often involves ring opening as a prominent excited-state relaxation pathway. The identification of this particular photoinduced mechanism, however, presents a challenge for many experimental methods. We show that femtosecond X-ray transient absorption spectroscopy at the carbon K-edge (~284 eV) provides core-to-valence spectral fingerprints that enable the unambiguous identification of ring-opened isomers of organic heterocycles. The unique differences in the electronic structure between a carbon atom bonded to the oxygen in the ring versus a carbon atom set free of the oxygen in the ring-opened product are readily apparent in the X-ray spectra. Ultrafast ring opening via C-O bond fission occurs within ~350 fs in 266-nm photoexcited furfural, as evidenced by fingerprint core (carbon 1s) electronic transitions into a nonbonding orbital of the open-chain carbene intermediate at 283.3 eV. The lack of recovery of the 1sπ* ground-state depletion in furfural at 286.4 eV indicates that internal conversion to the ground state is a minor channel. These experimental results, augmented by recent advances in the generation of isolated attosecond pulses at the carbon K-edge, will pave the way for probing ring-opened conical intersection dynamics in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Transient Absorption Spectroscopy Offers Mechanistic Insights for an Iridium/Nickel-Catalyzed C–O Coupling

We report mechanistic insights into an iridium/nickel photocatalytic C–O cross-coupling reaction from time-resolved spectroscopic studies. Using transient absorption spectroscopy, energy transfer from an iridium photocatalyst to a catalytically relevant Ni(II)(aryl) acetate acceptor was observed. Concentration-dependent lifetime measurements suggest the mechanism of the subsequent reductive elimination is a unimolecular process occurring on the long-lived excited state of the Ni(II) complex. Furthermore, we envision that our study of the productive energy-transfer-mediated pathway would encourage the development of new excited-state reactivities in the field of metallaphotocatalysis that are enabled by light harvesting.

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

Spacecraft-charging mitigation of a high-power electron beam emitted by a magnetospheric spacecraft: Simple theoretical model for the transient of the spacecraft potential

A spacecraft-charging mitigation scheme necessary for the operation of a high-power electron beam in the low-density magnetosphere is analyzed. The scheme is based on a plasma contactor, i.e. a high-density charge-neutral plasma emitted prior to and during beam emission, and its ability to emit high ion currents without strong space-charge limitations. A simple theoretical model for the transient of the spacecraft potential and contactor expansion during beam emission is presented. The model focuses on the contactor ion dynamics and is valid in the limit when the ion contactor current is equal to the beam current. The model is found in very good agreement with Particle-In-Cell simulations over a large parametric study that varies the initial expansion time of the contactor, the contactor current and the ion mass. The model highlights the physics of the spacecraft-charging mitigation scheme, indicating that the most important part of the dynamics is the evolution of the outermost ion front which is pushed away by the charge accumulated in the system by the beam. The model can be also used to estimate the long-time evolution of the spacecraft potential. For a short contactor expansion (0.3 or 0.6 ms Helium plasma or 0.8 ms Argon plasma, both with 1 mA current) it yields a peak spacecraft potential of the order of 1-3 kV. This implies that a 1-mA relativistic electron beam would be easily emitted by the spacecraft.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2019

Modeling Transient Soil Moisture Limitations on Microbial Carbon Respiration

Soil microorganisms are known to survive periods of aridity and to recover rapidly after wetting events, with the ability to transition between a dormant state in dry conditions and an active state in wet conditions. While this dynamic behavior has been previously incorporated into soil carbon respiration modeling frameworks, a direct comparison between this active-dormant transition mechanism and a more simplified first-order model has yet to be made. Here, we demonstrate the necessary extent of model complexity needed to reproduce transient carbon respiration rates obtained from a set of soil incubation experiments implemented over a range of soil depths and time intervals. Two approaches are tested, one uses simplified first-order kinetics, whereas the other employs a transition between active and dormant biomass. The performance of each model is evaluated using an Akaike Information Criterion (AIC) based on the accuracy with which they reproduce an experimental dataset consisting of two sets of time series soil incubations collected across a range of time and depth resolutions. Based on the AIC evaluation and model-data comparison, we conclude that a dormancy-enabled model featuring two distinct microbial strategists performs best for the majority of the soil profile (above 108 cm) for both high and low depth resolution and sampling frequency, despite the added parameters required. In contrast, the first-order model achieves better AIC scores when simulating our deepest soils (112–165 cm), where moisture fluctuations are expected to be less prevalent. These findings guide how and where we choose to apply more cost intensive models.

58 GEOSCIENCES↗
DOE OSTI2021

Biased Estimates of Equilibrium Climate Sensitivity and Transient Climate Response Derived From Historical CMIP6 Simulations

Abstract This study assesses the effective climate sensitivity (EffCS) and transient climate response (TCR) derived from global energy budget constraints within historical simulations of eight CMIP6 global climate models (GCMs). These calculations are enabled by use of the Radiative Forcing Model Intercomparison Project (RFMIP) simulations, which permit accurate quantification of the radiative forcing. Long‐term historical energy budget constraints generally underestimate EffCS from CO 2 quadrupling and TCR from CO 2 ramping, owing to changes in radiative feedbacks and changes in ocean heat uptake efficiency. Atmospheric GCMs forced by observed warming patterns produce lower values of EffCS that are more in line with those inferred from observed historical energy budget changes. The differences in the EffCS estimates from historical energy budget constraints of models and observations are traced to discrepancies between modeled and observed historical surface warming patterns.

Dong, Yue↗
DOE OSTI2021

A Data Set for Intercomparing the Transient Behavior of Dynamical Model-Based Subseasonal to Decadal Climate Predictions

Climate predictions using coupled models in different time scales, from intraseasonal to decadal, are usually affected by initial shocks, drifts, and biases, which reduce the prediction skill. These arise from inconsistencies between different components of the coupled models and from the tendency of the model state to evolve from the prescribed initial conditions toward its own climatology over the course of the prediction. Aiming to provide tools and further insight into the mechanisms responsible for initial shocks, drifts, and biases, this paper presents a novel data set developed within the Long Range Forecast Transient Intercomparison Project, LRFTIP. This data set has been constructed by averaging hindcasts over available prediction years and ensemble members to form a hindcast climatology, that is a function of spatial variables and lead time, and thus results in a useful tool for characterizing and assessing the evolution of errors as well as the physical mechanisms responsible for them. A discussion on such errors at the different time scales is provided along with plausible ways forward in the field of climate predictions

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Slow thermal equilibration in methylammonium lead iodide revealed by transient mid-infrared spectroscopy

Hybrid organic–inorganic perovskites are emerging semiconductors for cheap and efficient photovoltaics and light-emitting devices. Different from conventional inorganic semiconductors, hybrid perovskites consist of coexisting organic and inorganic sub-lattices, which present disparate atomic masses and bond strengths. The nanoscopic interpenetration of these disparate components, which lack strong electronic and vibrational coupling, presents fundamental challenges to the understanding of charge and heat dissipation. Here we study phonon population and equilibration processes in methylammonium lead iodide (MAPbI 3 ) by transiently probing the vibrational modes of the organic sub-lattice following above-bandgap optical excitation. We observe inter-sub-lattice thermal equilibration on timescales ranging from hundreds of pico seconds to a couple of nanoseconds. As supported by a two temperature model based on first-principles calculations, the slow thermal equilibration is attributable to the sequential phonon populations of the inorganic and organic sub-lattices, respectively. The observed long-lasting thermal non-equilibrium offers insights into thermal transport and heat management of the emergent hybrid material class.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2019

Disentangling conical intersection and coherent molecular dynamics in methyl bromide with attosecond transient absorption spectroscopy

Attosecond probing of core-level electronic transitions provides a sensitive tool for studying valence molecular dynamics with atomic, state, and charge specificity. In this report, we employ attosecond transient absorption spectroscopy to follow the valence dynamics of strong-field initiated processes in methyl bromide. By probing the 3d core-to-valence transition, we resolve the strong field excitation and ensuing fragmentation of the neutral σ* excited states of methyl bromide. The results provide a clear signature of the non-adiabatic passage of the excited state wavepacket through a conical intersection. We additionally observe competing, strong field initiated processes arising in both the ground state and ionized molecule corresponding to vibrational and spin-orbit motion, respectively. The demonstrated ability to resolve simultaneous dynamics with few-femtosecond resolution presents a clear path forward in the implementation of attosecond XUV spectroscopy as a general tool for probing competing and complex molecular phenomena with unmatched temporal resolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗