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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 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Efficient Free Triplet Generation Follows Singlet Fission in Diketopyrrolopyrrole Polymorphs with Goldilocks Coupling

Microcrystal electron diffraction, grazing incidence wide-angle scattering, and UV–vis spectroscopy were used to determine the unit-cell structure and the relative composition of dimethylated diketopyrrolopyrrole H- and J-polymorphs within thin films subjected to vapor solvent annealing (VSA) for different times. The electronic structure and excited-state deactivation pathways of the different polymorphs were examined by transient absorption spectroscopy, conductive probe atomic force microscopy, and molecular modeling. We find that VSA initially converts amorphous films into mixtures of H- and J-polymorphs and promotes further conversion from H to J with longer VSA times. Here, though both polymorphs exhibit efficient SF to form coupled triplets, free triplet yields are higher in J-polymorph films compared to mixed films because coupling in J-aggregates is lower and, in turn, more favorable for triplet decoupling.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Visualization of dynamic polaronic strain fields in hybrid lead halide perovskites

Excitation localization involving dynamic nanoscale distortions is a central aspect of photocatalysis, quantum materials and molecular optoelectronics. Experimental characterization of such distortions requires techniques sensitive to the formation of point-defect-like local structural rearrangements in real time. Here, we visualize excitation-induced strain fields in a prototypical member of the lead halide perovskites via femtosecond resolution diffuse X-ray scattering measurements. Here, this enables momentum-resolved phonon spectroscopy of the locally distorted structure and reveals radially expanding nanometre-scale strain fields associated with the formation and relaxation of polarons in photoexcited perovskites. Quantitative estimates of the magnitude and shape of this polaronic distortion are obtained, providing direct insights into the dynamic structural distortions that occur in these materials. Optical pump–probe reflection spectroscopy corroborates these results and shows how these large polaronic distortions transiently modify the carrier effective mass, providing a unified picture of the coupled structural and electronic dynamics that underlie the optoelectronic functionality of the hybrid perovskites.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Dissociative electron attachment to 5-bromo-uracil: non-adiabatic dynamics on complex-valued potential energy surfaces

Electron induced dissociation reactions are relevant to many fields, ranging from prebiotic chemistry to cancer treatments. However, the simulation of dissociation electron attachment (DEA) dynamics is very challenging because the auto-ionization widths of the transient negative ions must be accounted for. We propose an adaptation of the ab initio multiple spawning (AIMS) method for complex-valued potential energy surfaces, along the lines of recent developments based on surface hopping dynamics. Our approach combines models for the energy dependence of the auto-ionization widths, obtained from scattering calculations, with survival probabilities computed for the trajectory basis functions employed in the AIMS dynamics. The method is applied to simulate the DEA dynamics of 5-bromouracil in full dimensionality, i.e., taking all the vibrational modes into consideration. The propagation starts on the $π_{2}^{*}$ resonance state and describes the formation of Br - anions mediated by non-adiabatic couplings. The potential energies, gradients and non-adiabatic couplings were computed with the fractional-occupancy molecular orbital complete-active-space configuration-interaction method, and the calculated DEA cross section are consistent with the observed DEA intensities.

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

Analytical WKB theory for high-harmonic generation and its application to massive Dirac electrons

Here we propose an analytical approach to high-harmonic generation (HHG) for nonperturbative low-frequency and high-intensity fields based on the (Jeffreys-)Wentzel-Kramers-Brillouin (WKB) approximation. By properly taking into account Stokes phenomena of WKB solutions, we obtain wave functions that systematically include the repetitive dynamics of production and acceleration of electron-hole pairs and quantum interference due to phase accumulation between different pair production times (Stückelberg phase). Using the obtained wave functions without relying on any phenomenological assumptions, we explicitly compute electric current (including intra- and interband contributions) as the source of HHG for a massive Dirac system in (1+1) dimensions under an ac electric field. We demonstrate that the WKB approximation agrees well with numerical results obtained by solving the time-dependent Schrödinger equation and point out that the quantum interference is important in HHG. We also predict in the deep nonperturbative regime that (1) harmonic intensities oscillate with respect to electric-field amplitude E 0 and frequency Ω with a period determined by the Stückelberg phase, (2) the cutoff order of HHG is determined by 2eE 0 ℏΩ 2 , with e being the electron charge, and that (3) noninteger harmonics, controlled by the Stückelberg phase, appear as a transient effect. Our WKB theory is particularly suited for a parameter regime, where the Keldysh parameter γ = (Δ/2)Ω/eE 0 ,with Δ being the gap size, is small. This parameter regime corresponds to intense lasers in the terahertz regime for realistic massive Dirac materials. Our analysis implies that the so-called HHG plateau can be observed at the terahertz frequency within the current technology.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Transients using low-high pulsed power in inductively coupled plasmas

Pulsed inductively coupled plasmas (ICPs) are widely deployed in the fabrication of semi-conductor devices. Pulse repetition frequencies (PRFs) of up to tens of kHz are commonly used during plasma etching for the high power densities they generate during the pulse-on period, and for their unique chemistries during the pulse-off period. The use of highly attaching halogen gases produces low electron densities during the pulse-off period, and these low density can result in instabilities, E-H transitions and ignition delays when applying power on the next pulse. To mitigate these possibilities, a low-level power environment could be maintained during “pulse-off” to moderate the minimum plasma density, therefore reducing ignition delays and enhancing plasma stability. In this work, ICPs sustained by 5 kHz pulsed power using Ar/Cl 2 mixtures at 20 mTorr were computationally investigated. For these conditions, the computed electron temperature (T e ) reaches a quasi-steady state during both the high- and low-power excitation. The model predicts that within the electromagnetic skin-depth, T e spikes to a high value during a low-to-high power modulation, and to a low value during a high-to-low power modulation. At the same time, a few cm above the substrate, there is little modulation in T e , as electron power convected from the skin depth disperses in traversing the reactor. Finally, the positive and negative spikes, and convection of transients across the reactors, are functions of power ramping time and gas mixtures.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Charge carrier coupling to the soft phonon mode in a ferroelectric semiconductor

Many crystalline solids possess strongly anharmonic “soft” phonon modes characterized by diminishing frequency as temperature approaches a critical point associated with a symmetry breaking phase transition. While electron–soft phonon coupling can introduce unique scattering channels for charge carriers in ferroelectrics, recent studies on the nonferroelectric lead halide perovskites have also suggested the central role of anharmonic phonons bearing resemblance to soft modes in charge carrier screening. Here we apply coherent phonon spectroscopy to directly study electron coupling to the soft transverse optical phonon mode in a ferroelectric semiconductor SbSI. Photogenerated charge carriers in SbSI are found to be exceptionally long lived and are associated with a transient electro-optical effect that can be explained by interactions between charge carriers and thermally stimulated soft phonon excitations. Furthermore, these results provide strong evidence for the role of electron–soft phonon coupling in the efficient screening of charge carriers and in reducing charge recombination rates, both desirable properties for optoelectronics.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Transient gap generation in BaFe2As2 driven by coherent lattice vibrations

Abstract Iron-based superconductors provide a rich platform to investigate the interplay between unconventional superconductivity, nematicity, and magnetism. The electronic structure and the magnetic properties of iron-based superconductors are highly sensitive to the pnictogen height. Coherent excitation of the A1g phonon by femtosecond laser directly modulates the pnictogen height, which has been used to control the physical properties of iron-based superconductors. Previous studies show that the driven A1g phonon resulted in a transient increase of the pnictogen height in BaFe2As2, favoring an enhanced Fe magnetic moment. However, there are no direct observations on either the enhanced Fe magnetic moments or the enhanced spin-density wave (SDW) gap. Here, we use time-resolved broadband terahertz spectroscopy to investigate the dynamics of BaFe2As2 in the A1g phonon-driven state. Below the SDW transition temperature, we observe a transient gap generation at early-time delays. A similar transient feature is observed in the normal state up to room temperature.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Femtosecond Core-Level Spectroscopy Reveals Involvement of Triplet States in the Gas-Phase Photodissociation of Fe(CO) 5

Excitation of iron pentacarbonyl [Fe(CO) 5 ], a prototypical photocatalyst, at 266 nm causes the sequential loss of two CO ligands in the gas phase, creating catalytically active, unsaturated iron carbonyls. Despite numerous studies, major aspects of its ultrafast photochemistry remain unresolved because the early excited-state dynamics have so far eluded spectroscopic observation. This has led to the long-held assumption that ultrafast dissociation of gas-phase Fe(CO) 5 proceeds exclusively on the singlet manifold. Herein, we present a combined experimental–theoretical study employing ultrafast extreme ultraviolet transient absorption spectroscopy near the Fe M 2,3 -edge, which features spectral evolution on 100 fs and 3 ps time scales, alongside high-level electronic structure theory, which enables characterization of the molecular geometries and electronic states involved in the ultrafast photodissociation of Fe(CO) 5 . We assign the 100 fs evolution to spectroscopic signatures associated with intertwined structural and electronic dynamics on the singlet metal-centered states during the first CO loss and the 3 ps evolution to the competing dissociation of Fe(CO) 4 along the lowest singlet and triplet surfaces to form Fe(CO) 3 . Calculations of transient spectra in both singlet and triplet states as well as spin–orbit coupling constants along key structural pathways provide evidence for intersystem crossing to the triplet ground state of Fe(CO) 4 . Finally, our work presents the first spectroscopic detection of transient excited states during ultrafast photodissociation of gas-phase Fe(CO) 5 and challenges the long-standing assumption that triplet states do not play a role in the ultrafast dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Photoinduced Magnetic Exchange-Jump Promotes Ground State Biradical Electron Spin Polarization

Photoinduced electron spin polarization (ESP) is reported in the electronic ground states of three Pt(II) complexes that are comprised of two S = ½ nitronyl nitroxide (NN) radicals attached through different length para-phenylethynyl bridges to the 3,6 positions of a catecholate (CAT, donor) and 4,4’-di-tert-butyl-2,2’-bipyridine (bpy, acceptor). Complexes 1-3 have from 17 to 41 bonds separating NN radicals, and display cw-EPR spectra consistent with |J NN-NN | >> |a N |, |J NN-NN | ≥ |a N |, and |J NN-NN | < |a N |, respectively, where J NN-NN is the magnetic exchange coupling between NN radicals in the electronic ground state, and a N is the isotropic 14 N hyperfine coupling constant. Light-induced transient EPR spectra characterized as enhanced ground-state absorption were observed for all three complexes using 532 nm pulsed laser excitation into the ligand-to-ligand charge transfer (LL’CT) band of the (CAT)Pt(bpy) chromophore. The magnitude of the observed ESP increases in the order 1 < 2 < 3 and is inversely correlated with the magnitude of ground-state J NN-NN . In addition to the experimental observation net absorptive polarization in 1-3, light excitation also produces multiplet polarization in 2. Since the weak dipolar coupling leads to strong spectral overlap of the absorptive and emissive components, the multiplet polarization is not observed in 1 and 3 and is very weak in 2. Here, the ability to spin polarize multiple radical spins with a single photon is anticipated to advance new photoinduced multi qubit/qudit ESP protocols for quantum information science applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Dicyanobenzothiadiazole (DCBT) Organic Dye as a Visible Light Absorbing Strong Photoinduced Oxidant with a 16 Microsecond Long–Lived Excited State

Strong photoinduced oxidants are important to organic synthesis and solar energy conversion, to chemical fuels or electric. For these applications, visible light absorption is important to solar energy conversion and long–lived excited states are needed to drive catalysis. With respect to these desirable qualities, a series of five 5,6–dicyano[2,1,3]benzothiadiazole (DCBT) dyes are examined as organic chromophores that can serve as strong photooxidants in catalytic systems. The series utilizes a DCBT core with aryl groups on the periphery with varying electron donation strengths relative to the core. The dyes are studied via both steady–state and transient absorption and emission studies. Additionally, computational analysis, voltammetry, crystallography, and absorption spectroelectrochemistry are also used to better understand the behavior of these dyes. Ultimately, a strong photooxidant is arrived at with an exceptionally long excited state lifetime for an organic chromophore of 16 µs. Finally, the long–lived excited state photosensitizer is well–suited for use in catalysis, and visible light driven photosensitized water oxidation is demonstrated using a water–soluble photosensitizer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

A two-dimensional numerical study of ion-acoustic turbulence

We investigate the linear and nonlinear evolution of the current-driven ion-acoustic instability in a collisionless plasma via two-dimensional (2-D) Vlasov–Poisson numerical simulations. We initialise the system in a stable state and gradually drive it towards instability with an imposed, weak external electric field, thus avoiding physically unrealisable super-critical initial conditions. A comprehensive analysis of the nonlinear evolution of ion-acoustic turbulence (IAT) is presented, including the detailed characteristics of the evolution of the particles’ distribution functions, (2-D) wave spectrum and the resulting anomalous resistivity. Our findings reveal the dominance of 2-D quasi-linear effects around saturation, with nonlinear effects, such as particle trapping and nonlinear frequency shifts, becoming pronounced during the later stages of the system's nonlinear evolution. Remarkably, the Kadomtsev–Petviashvili (KP) spectrum is observed immediately after the saturation of the instability. Another crucial and noteworthy result is that no steady saturated nonlinear state is ever reached: strong ion heating suppresses the instability, which implies that the anomalous resistivity associated with IAT is transient and short-lived, challenging earlier theoretical results. Towards the conclusion of the simulation, electron-acoustic waves are triggered by the formation of a double layer and strong modifications to the particle distribution induced by IAT.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Substituent Effects on Transient, Carbodiimide-Induced Geometry Changes in Diphenic Acids

Nucleotide-induced conformational changes in motor proteins are key to many important cell functions. Inspired by this biological behavior, we report a simple chemically fueled system that exhibits carbodiimide-induced geometry changes. Bridging via transient anhydride formation leads to a significant reduction of the twist about the biaryl bond of substituted diphenic acids, giving a simple molecular clamp. The kinetics are well-described by a simple mechanism, allowing structure–property effects to be determined. The kinetic parameters can be used to derive important characteristics of the system such as the efficiencies (anhydride yields), maximum anhydride concentrations, and overall lifetimes. Transient diphenic anhydrides tolerate steric hindrance ortho to the biaryl bond but are significantly affected by electronic effects, with electron-deficient substituents giving lower yields, peak conversions, and lifetimes. Furthermore, the results provide useful guidelines for the design of functional systems incorporating diphenic acid units.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Controlling Fragmentation of the Acetylene Cation in the Vacuum Ultraviolet via Transient Molecular Alignment

An open-loop control scheme of molecular fragmentation based on transient molecular alignment combined with single-photon ionization induced by a short-wavelength free electron laser (FEL) is demonstrated for the acetylene cation. Photoelectron spectra are recorded, complementing the ion yield measurements, to demonstrate that such control is the consequence of changes in the electronic response with molecular orientation relative to the ionizing field. We show that stable C 2 H 2 + cations are mainly produced when the molecules are parallel or nearly parallel to the FEL polarization, while the hydrogen fragmentation channel (C 2 H 2 + → C 2 H + + H) predominates when the molecule is perpendicular to that direction, thus allowing one to distinguish between the two photochemical processes. The experimental findings are supported by state-of-the art theoretical calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Effects of Temperature Fluctuations on Surface Mobility of Atomic Steps and Oxidation Dynamics in High-Temperature Alloys

In contrast to the traditional perspective that thermal fluctuations are insignificant in surface dynamics, here we report their influence on surface reaction dynamics. Using real-time low-energy electron microscopy imaging of NiAl(100) under both vacuum and O 2 atmospheres, we demonstrate that transient temperature variations substantially alter the direction of atom diffusion between the surface and bulk, leading to markedly different oxidation outcomes. During heating, substantial outward diffusion of atoms from the bulk to the surface results in step growth. Conversely, cooling induces considerable inward diffusion of adatoms, producing a distinct oxide morphology. In both scenarios, initially formed oxide islands impede local atomic step mobility, thereby increasing step length due to mass transfer between the surface and bulk, with atomic steps acting as adatom sinks during heating and sources during cooling. Furthermore, we show that this pinning effect on atomic step mobility can be mitigated by applying persistent temperature fluctuations. As a result, understanding these nuances is vital for accurately predicting and dynamically manipulating the performance of active materials in various chemical processes under transient thermal conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Influence of substitution pattern on the dynamics of internal conversion and intersystem crossing in thiopyridone isomers

We report a combined experimental and theoretical investigation of the ultrafast internal conversion (IC) and intersystem crossing (ISC) dynamics of two thiopyridone (TP) isomers in solution. Our study used ultrafast transient X-ray absorption spectroscopy (XAS) at the sulfur K-edge, in conjunction with electronic excited state surface hopping molecular dynamics and simulations of the excited state XAS, to investigate the impact of the functional group substitution pattern and solvent on the dynamics of IC and ISC. The combination of the localized X-ray probe and the simulation results enables, in part, the differentiation between ππ* and nπ* character excited states, as well as singlet and triplet states. Access to nπ* character excitations has particular value since they often prove challenging to assess with optical spectroscopy. For 2-TP, the photoexcited S 2 (ππ*) state rapidly undergoes IC to the S 1 (nπ*) state below the instrument response time, followed by ISC to the T 1 (ππ*) state on a timescale of 600 fs in acetonitrile. For 4-TP, the timescale of S 2 to S 1 IC increases to 330 fs and the timescale of ISC increases to more than 10 ps. The differences between isomers are rationalized by considering the key role of the, nπ* intermediates in mediating the intersystem crossing of these systems. Varying the substitution pattern of the molecule can stabilize or destabilize these intermediates leading to the increase in ISC rate in the ortho isomer as compared to the para isomer, while changing the solvent from acetonitrile to water had minimal effect on the electronic excited state relaxation mechanism.

Garratt, Douglas [SLAC National Accelerator Labora↗
DOE OSTI2023

Self-consistent and detailed opacities from a non-equilibrium average-atom model

Modern density functional theory (DFT) is a powerful tool for accurately predicting self-consistent material properties such as equations of state, transport coefficients and opacities in high energy density plasmas, but it is generally restricted to conditions of local thermodynamic equilibrium (LTE) and produces only averaged electronic states instead of detailed configurations. We propose a simple modification to the bound-state occupation factor of a DFT-based average-atom model that captures essential non-LTE effects in plasmas—including autoionization and dielectronic recombination—thus extending DFT-based models to new regimes. Finally, we then expand the self-consistent electronic orbitals of the non-LTE DFT-AA model to generate multi-configuration electronic structure and detailed opacity spectra. This article is part of the theme issue ‘Dynamic and transient processes in warm dense matter’.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Dual-stage structural response to quenching charge order in magnetite

The Verwey transition in magnetite (Fe 3 O 4 ) is the prototypical metal-insulator transition and has eluded a comprehensive explanation for decades. A major element of the challenge is the complex interplay between charge order and lattice distortions. Here we use ultrafast electron diffraction (UED) to disentangle the roles of charge order and lattice distortions by tracking the transient structural evolution after charge order is melted via ultrafast photoexcitation. A dual-stage response is observed in which X 3 , X 1 and Δ 5 type structural distortions occur on markedly different timescales of 0.7-3.2 ps and longer than 3.2 ps. We propose that these distinct timescales arise because X 3 -type distortions strongly couple to the trimeron charge order whereas the Δ 5 -distortions are more strongly associated with monoclinic to cubic distortions of the overall lattice. Our work aids in clarifying the charge-lattice interplay using UED method and illustrates the disentanglement of the complex phases in magnetite.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Frequency Control and Disturbance Containment Using Grid-Forming Embedded Storage Networks

The paper presents a distributed approach for operating a network of inverter-based energy storage resources embedded in a bulk power system. Departing from their traditional role of steady-state reserves, the storage assets in the network are utilized as frequency-responsive resources shaping system dynamics. The power electronics converter systems interfacing the storage resources are equipped with local controllers designed to respond under transient disturbances. To this end, a safety-constrained distributed control strategy is explored. The paper compares the performance of converter-interfaced grid-forming and grid-following storage networks for fast frequency control and disturbance containment/localization. Sensitivity studies are performed to study the impact of storage size, steady-state dispatch, and controller design on dynamic performance. The findings are presented through case studies with results from the IEEE test systems.

Chatterjee, Kaustav (ORCID:0000000153273860)↗