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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Transient Symmetry Controls Photo Dynamics near Conical Intersections

Excited-state chemistry lacks generalised symmetry rules. With many femtochemistry studies focused on individual cases, it is hard to build up the same level of chemical intuition for excited-states as exists for ground states. Here, we unravel the degrees of freedom involved in ultrafast internal conversion (IC) by mapping the vibrational coherence of the initial wavepacket, and the dependence on molecular symmetry in various cyclic tertiary amines. Molecular symmetry plays an important role in the preservation of vibrational coherence in the transit from one electronic state to another. We show here that it is sufficient for the molecule to simply have the possibility of a more symmetric structure to achieve the preservation of vibrational coherence. It can be transient and still lead to preservation. Furthermore, this finding provides an additional angle on how symmetry influences electronic transitions and an additional piece to the puzzle of establishing symmetry-based selection rules for excited-state processes.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Above the Energy Gap Law: Heavy Chalcogenide Substitution in NIR II-Emissive Diradicaloid Qubits

Near-infrared (NIR, 700–1700 nm)- and telecom (∼1260–1625 nm)-emissive molecules are good candidates for biological imaging and quantum sensing applications, respectively; however, bright low energy emission is rare due to exponentially increasing nonradiative decay rates in these regions, a phenomenon known as the energy gap law. Recent literature has emphasized the importance of minimizing skeletal modes to prevent increased nonradiative decay rates, but most organic lumiphores in these regions utilize large, conjugated scaffolds containing many C═C modes. Here we report a compact, telecom-emissive scaffold, tetrathiafulvalene-2,3,6,7-tetraselenate, or TTFts, that displays remarkable air, water, and acid stability, exhibits record quantum yields and brightness values, and retains quantum coherence under ambient conditions. These properties are enabled through methodical selenium substitution, which bathochromically shifts emission while shifting skeletal vibrations to lower energies. This new scaffold validates heavy heteroatom substitution strategies and establishes a new class of bright telecom emitters and robust qubits.

biological imaging↗
DOE OSTI2021

Crystalline symmetry-protected non-trivial topology in prototype compound BaAl 4

The BaAl 4 prototype crystal structure is the most populous of all structure types, and is the building block for a diverse set of sub-structures including the famous ThCr 2 Si 2 family that hosts high-temperature superconductivity and numerous magnetic and strongly correlated electron systems. The MA 4 family of materials (M = Sr, Ba, Eu; A = Al, Ga, In) themselves present an intriguing set of ground states including charge and spin orders, but have largely been considered as uninteresting metals. We predict the exemplary compound BaAl 4 to harbor a three-dimensional Dirac spectrum with non-trivial topology and possible nodal lines crossing the Brillouin zone, wherein one pair of semi-Dirac points with linear dispersion along the k z direction and quadratic dispersion along the k x / k y direction resides on the rotational axis with C 4 v point group symmetry. An extremely large, unsaturating positive magnetoresistance in BaAl 4 despite an uncompensated band structure is revealed, and quantum oscillations and angle-resolved photoemission spectroscopy measurements confirm the predicted multiband semimetal structure with pockets of Dirac holes and a Van Hove singularity (VHS) remarkably consistent with the theoretical prediction. We thus present BaAl 4 as a topological semimetal, casting its prototype status into a role as a building block for a vast array of topological materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Amplified spontaneous emission from europium-based molecular complexes coupled to photonic crystal cavities

Rare-earth ion-based materials bear many remarkable optical properties that render them highly appealing for lighting and quantum-related applications. However, their small oscillator strength and weak emission often pose limitations. Here, in this work, we synthesize and couple Eu(III)-based molecular complexes to nanobeam photonic crystals supporting air modes. A reasonable spatial overlap between the molecular complexes and cavity modes leads to an average spontaneous emission coupling efficiency of 0.19. Our pump power-dependent photoluminescence measurements evidence amplified spontaneous emission from the molecular complexes with an amplification threshold as low as 4.4 W/cm 2 , likely benefiting from the efficient coupling. These findings suggest that integrating rare-earth ion-based molecular complexes with photonic structures could be a viable approach for regulating their emission characteristics for particular applications.

36 MATERIALS SCIENCE↗
DOE OSTI2025

On the functional dependence of transition-potential coupled cluster

Orbital relaxation of the core region is a primary source of error in the computation of core ionization and core excitation energies. Recently, Transition-Potential Coupled Cluster (TP-CC) methods have been used to explicitly treat orbital relaxation using non-variational molecular orbitals determined by reoccupation of orbitals optimized for a fractional core occupation. The amount of fractional occupation is governed by parameter λ, and recommended values for accurate TP-CCSD and XTP-CCSD computations of carbon, nitrogen, oxygen, and fluorine K edges were previously determined. Herein, we explore the performance of several density functionals for generating the fractionally occupied orbitals used in TP-CCSD. These functionals include HF, BP86, BH&HLYP, B3LYP, M06-2X, and ωB97m-V. The fractionally occupied orbitals computed across the various functionals were subsequently employed as the initial orbitals for our TP-CCSD calculations of organic K-edge x-ray absorption and photoelectron spectra. Regardless of the functional used to generate the fractionally occupied orbitals, the TP-CCSD calculations yield accurate and comparable core ionization energies, core excitation energies, and oscillator strengths.

Coupled-cluster methods↗
DOE OSTI2024

Stochastic modeling of x-ray superfluorescence

An approach to modeling the dynamics of x-ray amplified spontaneous emission and superfluorescence, the phenomenon of collective x-ray emission initiated by intense pulses of x-ray free-electron lasers, is developed based on stochastic partial differential equations. The equations are derived from first principles, and the relevant approximations, derivation steps, and extensions specific to stimulated x-ray emission are presented. The resulting equations take the form of three-dimensional generalized Maxwell-Bloch equations augmented with noise terms for both field and atomic variables. The derived noise terms possess specific correlation properties that enable the correct reconstruction of spontaneous emission. Consequently, the developed theoretical formalism is universally suitable for describing all stages of stimulated x-ray emission: spontaneous emission, amplified spontaneous emission, and superfluorescence. Here, we present numerical examples that illustrate various properties of the emitted field, including spatiotemporal coherence and spectral-angular and polarization characteristics. We anticipate that the proposed theoretical framework will establish a robust foundation for interpreting measurements in stimulated x-ray emission spectroscopy, modeling x-ray laser oscillators, and describing other experiments leveraging x-ray superfluorescence.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Fast redox switches lead to rapid transformation of goethite in humid tropical soils: A Mössbauer spectroscopy study

Abstract Humid tropical forest soils experience frequent rainfall, which limits oxygen diffusion and creates redox heterogeneity in upland soils. In this study we gauged the effect of short‐term anoxic conditions on Fe mineralogy of relatively Fe‐ and C‐rich surface soils (C/Fe mole ratio ∼5) from a humid tropical forest in Puerto Rico. Soils subjected to 4‐d oxic/anoxic oscillation were characterized by selective chemical extractions, Mössbauer spectroscopy (MBS), and X‐ray diffraction. Chemical extraction data suggested that rapidly switching redox conditions had subtle effects on bulk Fe mineralogy. Mössbauer, on the other hand, indicated that (a) the soil Fe is a mixture of goethites of varying characteristics with minor contributions from ferrihydrite (<5%) and Fe(III)‐organic matter (OM) phases (∼10%), and (b) anoxic conditions rapidly transformed all forms of goethite to relatively stable Fe oxides. Such fast changes in goethite features could be due to rapid depletion and sorption of bio‐released structural Al or sorbed OM onto residual soil components. The rapid temporal changes in MBS parameters and corresponding pore water nominal oxidation state of C values suggest that Fe‐C transformations in these upland tropical soils are complex and intricately coupled. A comprehensive understanding of the fate of Fe, Al, and OM (Fe‐organic moieties) during redox switches and concurrent changes in pore water chemistry is critical for development of robust transport models in humid tropical soils, which are subject to episodic low‐redox events.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

On the redistribution of charge in La 0.7 Sr 0.3 CrO 3 /La 0.7 Sr 0.3 MnO 3 multilayer thin films

The atomic and electronic structures of La 0.7 Sr 0.3 MnO 3 (LSMO)/La 0.7 Sr 0.3 CrO 3 (LSCO) multilayer thin films are investigated using aberration corrected scanning transmission electron microscopy (STEM) imaging and spectroscopy. Atomic resolution high angle annular dark-field reveals that LSMO layers have an expanded out-of-plane lattice parameter compared to compressed LSCO layers, contrasting with x-ray diffraction measurements. The expansion is found to result from preferential oxygen vacancy formation in LSMO during STEM sample preparation as determined by electron energy-loss spectroscopy. The La/Sr atom column intensity is also found to oscillate by about 4% between the LSMO and LSCO layers, indicative of La/Sr concentration variation. Using energy-dispersive x-ray spectroscopy in combination with image simulations, we confirm the La/Sr inhomogeneity and elucidate the origin of charge redistribution within the multilayer. These results illuminate the sensitivity of the technique to subtle structural, chemical, and electronic features that can arise to compensate charge imbalances in complex oxide heterostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Mock data sets for the Eboss and DESI Lyman-α forest surveys

We present a publicly-available code to generate sets of mock Lyman-α (Lyα) forest data that have realistic large-scale correlations including those due to the Baryonic Acoustic Oscillations (BAO). The primary purpose of these mocks is to test the analysis procedures of the Extended Baryon Oscillation Survey (eBOSS) and the Dark Energy Spectroscopy Instrument (DESI) surveys. The transmitted flux fraction, F(λ), of background quasars due to Lyα absorption in the intergalactic medium (IGM) is simulated using the Fluctuating Gunn-Petterson Approximation (FGPA) applied to Gaussian random fields produced through the use of fast Fourier transforms (FFT). The output includes the IGM-Lyα transmitted flux fraction along quasar lines of sight and a catalog of high-column-density systems appropriately placed at high-density regions of the IGM. This output serves as input to additional code that superimposes the IGM tranmission on realistic quasar spectra, adds absorption by high-column-density systems and metals, and simulates instrumental transmission and noise. Redshift space distortions (RSD) of the flux correlations are implemented by including the large-scale velocity-gradient field in the FGPA resulting in a correlation function of F(λ) that can be accurately predicted. One hundred realizations have been produced over the 14,000 deg 2 DESI survey footprint with 100 quasars per deg 2 . The analysis of these realizations shows that the correlations of F(λ) follows the prediction within the accuracy of eBOSS survey. Here, the most time-consuming part of the mock production occurs before application of the FGPA, and the existing pre-FGPA forests can be used to easily produce new mock sets with modified redshift-dependent bias parameters or observational conditions.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Platinum Graphene Catalytic Condenser for Millisecond Programmable Metal Surfaces

Accelerating catalytic chemistry and tuning surface reactions require precise control of the electron density of metal atoms. In this work, nanoclusters of platinum were supported on a graphene sheet within a catalytic condenser device that facilitated electron or hole accumulation in the platinum active sites with negative or positive applied potential, respectively. The catalytic condenser was fabricated by depositing on top of a p-type Si wafer an amorphous HfO 2 dielectric (70 nm), on which was placed the active layer of 2–4 nm platinum nanoclusters on graphene. A potential of ±6 V applied to the Pt/graphene layer relative to the silicon electrode moved electrons into or out of the active sites of Pt, attaining charge densities more than 1% of an electron or hole per surface Pt atom. At a level of charge condensation of ±10% of an electron per surface atom, the binding energy of carbon monoxide to a Pt(111) surface was computed via density functional theory to change 24 kJ mol –1 (0.25 eV), which was consistent with the range of carbon monoxide binding energies determined from temperature-programmed desorption (ΔBE CO of 20 ± 1 kJ mol –1 or 0.19 eV) and equilibrium surface coverage measurements (ΔBE CO of 14 ± 1 kJ mol –1 or 0.14 eV). Impedance spectroscopy indicated that Pt/graphene condensers with potentials oscillating at 3000 Hz exhibited negligible loss in capacitance and charge accumulation, enabling programmable surface conditions at amplitudes and frequencies necessary to achieve catalytic resonance.

Inorganic carbon compounds↗
DOE OSTI2020

Momentum-resolved analysis of condensate dynamic and Higgs oscillations in quenched superconductors with time-resolved ARPES

Higgs oscillations in nonequilibrium superconductors provide a unique tool to obtain information about the underlying order parameter. Several properties like the absolute value, existence of multiple gaps, and the symmetry of the order parameter can be encoded in the Higgs oscillation spectrum. Studying Higgs oscillations with time-resolved angle-resolved photoemission spectroscopy (ARPES) has the advantage over optical measurements that a momentum-resolved analysis of the condensate dynamic is possible. In this paper, we investigate the time-resolved spectral function measured in ARPES for different quench protocols. We find that analyzing amplitude oscillations of the ARPES intensity in the whole Brillouin zone allows to understand how the condensate dynamic contributes to the emerging of collective Higgs oscillations. Furthermore, by evaluating the phase of these oscillations, the symmetry deformation dynamic of the condensate can be revealed, which gives insight about the ground state symmetry of the system. With such an analysis, time-resolved ARPES experiments might be used in the future as a powerful tool in the field of Higgs spectroscopy.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Biexciton and trion dynamics in InP/ZnSe/ZnS quantum dots

Transient absorption (TA) and time-resolved photoluminescence (PL) spectroscopies have been used to elucidate the hole tunneling and Auger dynamics in biexcitons and negative trions in high-quality InP/ZnSe/ZnS quantum dots (QDs). In a previous paper [Nguyen et al., J. Phys. Chem. C 125, 15405–15414 (2021)], we showed that under high-intensity photoexcitation, two types of biexcitons are formed: those having two conduction band electrons and two valence band holes (designated as an XX state) and those having two conduction band electrons, one valence band hole, and an additional trapped hole (designated as an XT state). In the present paper, we show that both types of biexcitons can undergo Auger processes, with those of the XT state being a factor of four to five slower than those of the XX state. In addition, the trapped holes can undergo tunneling into the valence band, converting an XT state to an XX state. The relative amplitudes of the fast (XX) and slow (XT) components are different in the TA and PL kinetics, and these differences can be quantitatively understood in terms of oscillator strengths and electron–hole overlap integrals of each state. XT to XX hole tunneling rates are obtained from the comparison of the XT state lifetimes with those of the negative trions. This comparison shows that the tunneling times decrease with decreasing core size and shell thickness. Furthermore, these times are about 2 ns for the thinnest shell red-emitting QDs and decrease to 330 ps for QDs that luminesce in the yellow.

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

Room‐Temperature Mid‐Infrared Detection Using Metasurface‐Absorber‐Integrated Phononic Crystal Oscillator

Mid-infrared (MIR) detectors find extensive applications in chemical sensing, spectroscopy, communications, biomedical diagnosis, and space exploration. Alternative to semiconductor MIR photodiodes and bolometers, mechanical-resonator-based MIR detectors show advantages in higher sensitivity and lower noise at room temperature, especially toward longer wavelength infrared. Here, uncooled room-temperature MIR detectors based on lithium niobate surface acoustic wave phononic crystal (PnC) resonators integrated with wavelength-and-polarization-selective metasurface absorber arrays are demonstrated. The detection is based on the resonant frequency shift induced by the local temperature change due to MIR absorptions. The PnC resonator is configured in an oscillating mode, enabling active readout and low-frequency noise. The 1-GHz oscillator-based MIR detector shows a relative frequency deviation of 5.24 × 10 −10 Hz −1/2 at an integration time of 50 µs, leading to an incident noise equivalent power of 197 pW Hz −1/2 when input 6-µm MIR light is modulated at 1.8 kHz, and a large dynamic range of 10 7 in incident MIR power. The device architecture is compatible with the scalable manufacturing process and can be readily extended to a broader spectral range by tailoring the absorbing wavelengths of metasurface absorbers.

Xi, Zichen [Virginia Polytechnic Inst. and State U↗
DOE OSTI2020

Computationally Guided Investigation of the Optical Spectra of Pure β-UO 3

Single-phase β-UO 3 is synthesized by flash heating UO 2 (NO 3 )·6H 2 O in air to 450 °C and annealing for 60 h under the same conditions. For the first time, we report the Raman spectra of pure β-UO 3 . To facilitate the assignment of Raman and infrared vibrational modes, we use density functional theory with density functional perturbation theory. By employing a novel analysis scheme that includes the mode frequencies as well as a quantitative analysis of the mode eigenvectors, we assign the observed spectral features to individual chemical modes. In particular, the density functional theory optimized structure, observed Raman spectrum, and eigenvector analysis suggest the presence of four crystallographically distinct uranyl ions, one more than has previously been suggested.

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

Light quantum control of persisting Higgs modes in iron-based superconductors

The Higgs mechanism, i.e., spontaneous symmetry breaking of the quantum vacuum, is a cross-disciplinary principle, universal for understanding dark energy, antimatter and quantum materials, from superconductivity to magnetism. Unlike one-band superconductors (SCs), a conceptually distinct Higgs amplitude mode can arise in multi-band, unconventional superconductors via strong interband Coulomb interaction, but is yet to be accessed. Here we discover such hybrid Higgs mode and demonstrate its quantum control by light in iron-based high-temperature SCs. Using terahertz (THz) two-pulse coherent spectroscopy, we observe a tunable amplitude mode coherent oscillation of the complex order parameter from coupled lower and upper bands. The nonlinear dependence of the hybrid Higgs mode on the THz driving fields is distinct from any known SC results: we observe a large reversible modulation of resonance strength, yet with a persisting mode frequency. Together with quantum kinetic modeling of a hybrid Higgs mechanism, distinct from charge-density fluctuations and without invoking phonons or disorder, our result provides compelling evidence for a light-controlled coupling between the electron and hole amplitude modes assisted by strong interband quantum entanglement. Such light-control of Higgs hybridization can be extended to probe many-body entanglement and hidden symmetries in other complex systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Kramers nodal lines in intercalated TaS 2 superconductors

Kramers degeneracy is one fundamental embodiment of the quantum mechanical nature of particles with half-integer spin under time reversal symmetry. Under the chiral and noncentrosymmetric achiral crystalline symmetries, Kramers degeneracy emerges respectively as topological quasiparticles of Weyl fermions and Kramers nodal lines (KNLs), anchoring the Berry phase-related physics of electrons. However, an experimental demonstration for ideal KNLs well isolated at the Fermi level is lacking. Here, we establish a class of noncentrosymmetric achiral intercalated transition metal dichalcogenide superconductors with large Ising-type spin-orbit coupling, represented by In x TaS 2 , to host an ideal KNL phase. We provide evidence from angle-resolved photoemission spectroscopy with spin resolution, angle-dependent quantum oscillation measurements, and ab-initio calculations. Our work not only provides a realistic platform for realizing and tuning KNLs in layered materials, but also paves the way for exploring the interplay between KNLs and superconductivity, as well as applications pertaining to spintronics, valleytronics, and nonlinear transport.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A generalized class of strongly stable and dimension-free T-RPMD integrators

Here, recent work shows that strong stability and dimensionality freedom are essential for robust numerical integration of thermostatted ringpolymer molecular dynamics (T-RPMD) and path-integral molecular dynamics, without which standard integrators exhibit non-ergodicity and other pathologies [R. Korol et al., J. Chem. Phys. 151, 124103 (2019) and R. Korol et al., J. Chem. Phys. 152, 104102 (2020)]. In particular, the BCOCB scheme, obtained via Cayley modification of the standard BAOAB scheme, features a simple reparametrization of the free ring-polymer sub-step that confers strong stability and dimensionality freedom and has been shown to yield excellent numerical accuracy in condensed-phase systems with large time steps. Here, we introduce a broader class of T-RPMD numerical integrators that exhibit strong stability and dimensionality freedom, irrespective of the Ornstein–Uhlenbeck friction schedule. In addition to considering equilibrium accuracy and time step stability as in previous work, we evaluate the integrators on the basis of their rates of convergence to equilibrium and their efficiency at evaluating equilibrium expectation values. Within the generalized class, we find BCOCB to be superior with respect to accuracy and efficiency for various configuration-dependent observables, although other integrators within the generalized class perform better for velocity-dependent quantities. Extensive numerical evidence indicates that the stated performance guarantees hold for the strongly anharmonic case of liquid water. Both analytical and numerical results indicate that BCOCB excels over other known integrators in terms of accuracy, efficiency, and stability with respect to time step for practical applications.

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

Non-Kasha fluorescence of pyrene emerges from a dynamic equilibrium between excited states

Pyrene fluorescence after a high-energy electronic excitation exhibits a prominent band shoulder not present after excitation at low energies. The standard assignment of this shoulder as a non-Kasha emission from the second-excited state (S 2 ) has been recently questioned. To elucidate this issue, we simulated the fluorescence of pyrene using two different theoretical approaches based on vertical convolution and nonadiabatic dynamics with nuclear ensembles. To conduct the necessary nonadiabatic dynamics simulations with high-lying electronic states and deal with fluorescence timescales of about 100 ns of this large molecule, we developed new computational protocols. The results from both approaches confirm that the band shoulder is, in fact, due to S 2 emission. We show that the non-Kasha behavior is a dynamic-equilibrium effect not caused by a metastable S 2 minimum. However, it requires considerable vibrational energy, which can only be achieved in collisionless regimes after transitions into highly excited states. This strict condition explains why the S 2 emission was not observed in some experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗