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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Elementary excitations of a system of one-dimensional chiral fermions with short-range interactions

Here, we study general features of the excitation spectrum of a system of one-dimensional chiral spinless fermions with short-range interactions. We show that the nature of the elementary excitations of such a system depends strongly on the nonlinearity of the underlying dispersion of the fermions. In the case of quadratic nonlinearity, the low-momentum excitations are essentially fermionic quasiparticles and quasiholes, whereas the high-momentum ones are classical harmonic waves and solitons. In the case of cubic nonlinearity, the nature of the elementary excitations does not depend on momentum and is determined by the strength of the interactions. At a certain critical value of the interaction strength, the excitation spectrum changes qualitatively, pointing to a dynamic phase transition in the system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Experimental determination of shock speed versus exciter speed in a two-dimensional dusty plasma

A shock that is continuously driven by a moving exciter will propagate at a speed that depends on the exciter speed. We obtained this dependence experimentally, in a strongly coupled dusty plasma that was prepared as a single two-dimensional layer of charged microparticles. Attaining this result required an experimental advance, developing a method of driving a shock continuously, which we did using an exciter moving at a constant supersonic speed, analogous to a piston in a cylinder. The resulting compressional pulse was a shock that propagated steadily without weakening, ahead of the moving exciter. In this work, we compare our experimental results to an empirical form $M_{\text{shock}} = 1 + sM_{\text{exciter}}$, and to the prediction of a recent simulation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Autoionization and Dressing of Excited Excitons by Free Carriers in Monolayer WSe 2

We experimentally demonstrate dressing of the excited exciton states by a continuously tunable Fermi sea of free charge carriers in a monolayer semiconductor. It represents an unusual scenario of two-particle excitations of charged excitons previously inaccessible in conventional material systems. We identify excited state trions, accurately determine their binding energies in the zero-density limit for both electron- and hole-doped regimes, and observe emerging many-body phenomena at elevated doping. Combining experiment and theory we gain access to the intra-exciton coupling facilitated by the interaction with free charge carriers. We provide evidence for a process of autoionization for quasiparticles, a unique scattering pathway available for excited states in atomic systems. Finally, we demonstrate a complete transfer of the optical transition strength from the excited excitons to dressed Fermi-polaron states as well as the associated light emission from their nonequilibrium populations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Simple self-consistent method for excited states in density functional theory to characterize defect-derived behavior in wide-band-gap-based microelectronic materials

This final report summarizes the results of the Laboratory Direct Research and Development (LDRD) Project Number 229740. Wide band gap semiconductors such as gallium nitride (GaN) have features highly desirable for multiple mission electronic applications. Realization of their potential requires atomic-scale understanding of electronic behavior. The principal experimental tools for electronically probing defects in GaN are chemically undifferentiating and lack a practical theoretical counterpart needed to identify and characterize specific defects. This project investigated whether a simple idea for modeling defect excited states and their associated photoluminescence (PL) energies is viable, as a path to accelerate the understanding of defect behavior and gain valuable insights into engineering new electronic materials and devices. The research implemented a non-self-consistent total-energy evaluation of a Koopmans-type estimation of an excited electronic state energy in density functional theory (DFT) calculations, and proceeded to design, implement, and assess a self-consistent method for computing excited states based upon an OCcupation-Constrained-DFT (occ-DFT). The occ-DFT was verified in test calculations of defect excited states and validated against well-characterized PL data for 3d transition metal defects in GaN. The method proved stable and robust in computing excited states and gave accurate predictions compared to experimental PL data. The combined ground state/excited-state capability proved capable of chemically differentiating defect species in GaN. In application to 3d dopants in GaN, we reinterpreted extensive experimental literature, proposed new defects as prospective candidates for use in quantum information applications, and outlined design strategies to create and exploit these potentially useful functional defects in GaN.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Symmetry Breaking in the Lowest-Lying Excited-State of CCl4: Valence Shell Spectroscopy in the 5.0–10.8 eV Photon Energy Range

We report absolute high-resolution vacuum ultraviolet (VUV) photoabsorption cross-sections of carbon tetrachloride (CCl4) in the photon energy range 5.0–10.8 eV (248–115 nm). The molecular spectrum and electronic structure have been comprehensively investigated together with quantum chemical calculations, providing geometries, bond lengths, vertical excitation energies and oscillator strengths. The major electronic excitations have been assigned to valence and Rydberg transitions which are also accompanied by vibrational excitation assigned to degenerate stretching, v3′t2 and degenerate deformation v4′t2 modes. The rather complex nuclear dynamics along the degenerate deformation mode, v4′t2, have been thoroughly investigated by Time-Dependent Density Functional Theory (TD-DFT) method. The relevant Jahn–Teller distortion operative within the lowest-lying electronic excited-state is shown here for the first time in order to yield a weak absorption feature at 6.156 eV. Further calculations on the potential energy curves for the singlet excited-states along the C–Cl stretching coordinate show the relevance of efficient C–Cl bond excision.

Biochemistry & Molecular Biology↗
DOE OSTI2021

Generation of excited species in a streamer discharge

At or near atmospheric pressure, most transient discharges, particularly in molecular gases or gas mixture containing molecular gases result in a space-charge dominated transport called a streamer discharge. The excited species generation in such discharges forms the basis for plasma chemistry in most technological applications. In this paper we simulate the propagation of streamers in atmospheric pressure N 2 to understand the energy partitioning in the formation of various excited species and compare the results to a uniform Townsend discharge. The model is fully two-dimensional with azimuthal symmetry. Results show a significantly larger fraction of the energy goes into vibrational excitation of the N 2 ground state in a streamer-type discharge in comparison to a Townsend discharge. For lower applied voltages, the anode-directed (negative) steamer is slightly more efficient in channeling energy for excited species production in comparison to a cathode-directed (positive) streamer. Near 70% overvoltage both types of streamers show very similar energy partitioning but quite different from a Townsend discharge.

42 ENGINEERING↗
DOE OSTI2022

Modeling of the effects of non-equilibrium excitation and electrode geometry on H 2 /air ignition in a nanosecond plasma discharge

In this work, we present the results of two-dimensional modeling of the effects of non-equilibrium excitation and electrode geometry on H 2 /air ignition in a nanosecond plasma discharge. A multiscale adaptive reduced chemistry solver for plasma assisted combustion (MARCS-PAC) based on PASSKEy discharge modeling package and compressible multi-component reactive flow solver ASURF+ is developed and validated. This model is applied to simulate the impact of non-equilibrium plasma excitation and electrode geometry and heat loss on the dynamics of the discharge from streamer to spark and ignition kernel development in a H 2 /air mixture with a pair of cylindrical electrodes. The results show that the plasmagenerated species (N 2 (A), N 2 (B), N 2 (a'), N 2 (C), O( 1 D), O and H) in the spark and afterglow significantly accelerate the ignition kernel development. The increase of discharge voltage at the same total discharge energy promotes the non-equilibrium active species production. It is found that the production of electronically excited species at higher reduced electric field strength is more efficient in enhancing ignition in comparison to the vibrational excitation and heating. Moreover, the 2D simulation clearly reveals that the electric field and active species distribution are highly non-uniform. The streamers are initiated at the sharp outer edges of the negative and positive electrodes by a strong electric field while the electric field is much weaker at the centerline of the electrodes. Furthermore, the simulations reveal that the ignition enhancement is sensitive to the variation of electrode shape, diameter, and gap size due to the changes of electric field distribution and location of streamer formation. A cylindrical electrode produces a larger discharge volume and ignition kernel than the parabolic and spherical electrodes, when the discharge is localized near the axis of the gap. It is found that there is a non-monotonic dependence of ignition kernel size on the electrode diameter and inter-electrode distance. The increase of electrode diameter and gap size above the optimal conditions leads to the reduction of ignition kernel volume, due to the decrease of active species concentration and gas temperature. At a larger electrode surface area and electrode diameter as well as smaller electrode gap size, the heat loss to electrode plays a greater role in reducing the ignition kernel size and slowing ignition kernel development. This work provides insights and guidance to understand the kinetic enhancement of non-equilibrium plasma and the effects of electrode geometries on ignition for the optimization ignitors in advanced engines.

42 ENGINEERING↗
DOE OSTI2021

OC6 Phase Ib: Validation of the CFD predictions of difference-frequency wave excitation on a FOWT semisubmersible

During the previous OC5 11 project, state-of-the-art mid-fidelity engineering tools for floating wind systems were found to consistently underpredict the nonlinear, low-frequency responses of semisubmersible offshore wind platforms, leading to substantial errors in the structural loads because of low-frequency surge and pitch resonance. To examine this underprediction, a coordinated investigation with computational fluid dynamics (CFD) simulations and model-basin experiments was carried out. Both investigations involved a fixed and simplified OC5-DeepCwind semisubmersible in bichromatic waves. The wave excitations - especially the nonlinear, difference-frequency excitation - on the structure from the CFD simulations were compared to the experimental measurements for validation, with uncertainty analyses for both the experimental and the CFD results. Furthermore, the wave excitations on each column of the semisubmersible were measured separately in the experiment, allowing the validation of the CFD results to be done on a per-column basis. Overall, the CFD predictions of the difference-frequency excitations agree with the experimental measurements, suggesting the CFD solutions can be used as a reference for tuning and improving the engineering-level tools and can provide a means to better understand the underprediction at low frequencies.

16 TIDAL AND WAVE POWER↗
DOE OSTI2025

Ambient Synthesis for Fe(II) Polypyridyl Complexes with an Order of Magnitude Increase in Charge-Transfer Excited-State Lifetimes over [Fe(bpy) 3 ] 2+

Replacing precious metals with abundant metals is an important research focus in photochemical energy conversion and storage to meet global energy demands. However, transition metal complexes (TMCs) based on abundant 3d metals typically possess photochemical disadvantages─such as short charge-transfer excited-state lifetimes─and molecular modifications have focused on optimizing the interplay of structure, dynamics, and energetics to overcome their limitations. One strategy to do so is the use of bespoke ligands that can extend the lifetimes of chemically useful excited states. Here, in this study, we report the synthesis and characterization of novel Fe(II) complexes featuring lengthy polypyridyl ligands that can be readily synthesized. Steady-state and transient absorption spectroscopies indicate that these complexes have desirable properties and their excited metal-to-ligand charge-transfer states live an order of magnitude longer than in the benchmark [Fe(bpy) 3 ] 2+ . This lifetime is largely preserved in the heteroleptic complexes, thereby enabling the preparation of asymmetric complexes. Additionally, we apply nonradiative transition theory to explain the long-time decay kinetics. In light of their ease of preparation and reasonable excited-state lifetimes, we suggest the use of these complexes in Fe(II) dye-sensitized solar cells, where the rate of charge injection would be competitive with increased lifetime.

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

I ntera C hem : Exploring Excited States in Virtual Reality with Ab Initio Interactive Molecular Dynamics

InteraChem is an ab initio interactive molecular dynamics (AI-IMD) visualizer that leverages recent advances in virtual reality hardware and software, as well as the graphical processing unit (GPU)-accelerated TeraChem electronic structure package, in order to render quantum chemistry in real time. We introduce the exploration of electronically excited states via AI-IMD using the floating occupation molecular orbital-complete active space configuration interaction method. The optimization tools in InteraChem enable identification of excited state minima as well as minimum energy conical intersections for further characterization of excited state chemistry in small- to medium-sized systems. We demonstrate that finite-temperature Hartree–Fock theory is an efficient method to perform ground state AI-IMD. InteraChem allows users to track electronic properties such as molecular orbitals and bond order in real time, resulting in an interactive visualization tool that aids in the interpretation of excited state chemistry data and makes quantum chemistry more accessible for both research and educational purposes.

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

Improving Excited-State Potential Energy Surfaces via Optimal Orbital Shapes

In this work, we demonstrate that, rather than resorting to high-cost dynamic correlation methods, qualitative failures in excited-state potential energy surface predictions can often be remedied at no additional cost by ensuring that optimal molecular orbitals are used for each individual excited state. This approach also avoids the weighting choices required by state-averaging and dynamic weighting and obviates their need for expensive wave function response calculations when relaxing excited-state geometries. Although multistate approaches are of course preferred near conical intersections, other features of excited-state potential energy surfaces can benefit significantly from our single-state approach. In three different systems, including a double bond dissociation, a biologically relevant amino hydrogen dissociation, and an amino-to-ring intramolecular charge transfer, we show that state-specific orbitals offer qualitative improvements over the state-averaged status quo.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Excited State Dynamics of a Conformationally Fluxional Copper Coordination Complex

The conversion of solar energy into chemical fuel represents a capstone goal of the 21st century and has the potential to supply terawatts of power in a globally distributed manner. However, the disparate time scales of photodriven charge separation (~fs) and steps in chemical reactions (~μs) represent an inherent bottleneck in solar-to-fuels technology. Here to address this discrepancy, we are developing earth-abundant coordination complexes that undergo light-induced conformational rearrangements such that charge separation (CS) is hastened, while charge recombination (CR) is slowed. To these ends, we report the preparation and characterization of a new series of conformationally fluxional copper coordination complexes that contain a twisted intramolecular charge transfer (TICT) fluorophore as part of their ligand scaffold. Structural and spectroscopic characterization of the Cu(I) and Cu(II) complexes formed with these ligands in their ground states establish oxidation state-dependent conformational dynamicity, while time-resolved emission and transient absorption spectroscopies define the photopysical parameters of photo-induced excited states. Building on initial reports with a related set of molecules, the improved ligand design presented here greatly simplifies the observed photophysics, effectively shutting down unwanted ligand-centered excited states previously observed. Finally, time-dependent density functional theory (TDDFT) analyses reveal an unusual metal-to-TICT electronic transition only reported once before, and though the formation of a CS state is not observed directly through experiments, TDDFT geometry optimizations in the excited states support the formation of transient Cu(II) CS species, lending credence to the potential success of our approach. These studies establish a clear model for the excited state dynamics at play in proof-of-concept systems and clarify key design parameters for future optimizations toward achieving long-lived CS via photoinduced conformational gating.

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

Role of the Character of the Excited State of Singly Reduced Rh 2 (II,II) Intermediates on Photocatalytic Activity

Singly reduced intermediates have recently been implicated as photoactive intermediates in a number of important reactions; however, their photophysical properties remain poorly understood. A series of dirhodium(II,II) complexes, cis-[Rh 2 (p-R-Form) 2 (bncn) 2 ] 2+ (bncn = benzo[c]cinnoline; p-R-Form = N,N′-di-p-R-phenylformamidinate), where R = −OCH 3 (1), −CH 3 (2), −H (3), −F (4), −Cl (5), and −CF 3 (6), and their respective radical anions were prepared and their excited state properties were investigated. Complex 3 acted as a singlemolecule photocatalyst for H 2 production with red light. Substitution on the formamidinate ligands in 1−6 affected the energy of the Rh 2 (δ*)/Form(π,nb) highest occupied molecular orbital (HOMO), consistent with the metal/ligand-to-ligand charge transfer ( 1 ML-LCT) absorption maxima and the 3 ML-LCT excited state lifetime, ranging from 1.6 ns in 1 to 54 ns in 6 in CH 3 CN. The highest turnover number for photocatalytic H 2 evolution was observed for 3, and the lowest values were for 1 and 6. The radical anion, [Rh 2 ] − , formed during photocatalysis, was shown to absorb a photon and undergo a second reduction. The lifetimes of the doublet excited states of [3] − and [6] − were 0.49 and 0.24 ns, respectively. Calculations showed that the lowest energy excited state in [3] − was 2 ML-LCT, whereas that in [6] − was a bncn − → Rh 2 (σ*) ligand-to-metal charge transfer ( 2 LMCT) state. The 2 LMCT state stabilized across the series from [1] − to [6] − , pointing at its role in modulating the photophysical properties. This work highlights the importance of the reductive quenching of [Rh 2 ] − and the generation of the doubly reduced species to effectively catalyze hydrogen evolution.

Absorption↗
DOE OSTI2021

Excited states in variational Monte Carlo using a penalty method

Here, in this article, the authors present a technique using variational Monte Carlo to solve for excited states of electronic systems. This technique is based on enforcing orthogonality to lower energy states, which results in a simple variational principle for the excited states. Energy optimization is then used to solve for the excited states. This technique is applied to the well-characterized benzene molecule, in which ~10 000 parameters are optimized for the first 12 excited states. Agreement within ~0.2 eV is obtained with higher scaling coupled cluster methods; small disagreements with experiment are likely due to vibrational effects.

36 MATERIALS SCIENCE↗
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↗
DOE OSTI2025

Excited electronic states of Na 2 and K 2 : The potential for long-lived “reservoir” states leading to collision induced population inversions

Potential energy curves (PECs) for the spin-free (ΛS) and spin–orbit (Ω) states associated with the four lowest-lying dissociation channels of Na 2 and K 2 were calculated at the SA-CASSCF/SO-CASPT2/aug-cc-pwCVQZ-DK level. The PECs of Na 2 were consistent with the experimental data and with the FS-CCSD (2,0) calculations, reproducing the double-well and the “shelf” character for some of the potentials of the excited states. For K 2 , the PECs behaved in a similar way and the spectroscopic parameters for the ground and the excited states are in good agreement with the available experimental values. The dissociation energy of K 2 was predicted to be D e = 4454 cm −1 , within an agreement of 5 cm −1 with the experiments. For Na 2 , D e = 5789 cm −1 compared to the experimental value of 6022 cm −1 . The inclusion of spin–orbit coupling effects resulted in avoided crossings, which affect the PECs. Spin–orbit changes the predicted curves for some excited Ω states arising from ΛS states that overlap each other, affecting their associated vibrational frequencies and bond distances. Here, the current studies of the low-lying states in K 2 reveal a similar structure to those of Na 2 , which suggests the accessibility of long-lived energy storing reservoir states and possible population inversions in K 2 following prior experimental work on the reaction of halogen atoms with Na 3 to produce excited states of Na 2 .

Ab-initio methods↗
DOE OSTI2023

Deconstructing magnetization noise: Degeneracies, phases, and mobile fractionalized excitations in tetris artificial spin ice

Direct detection of spontaneous spin fluctuations, or “magnetization noise,” is emerging as a powerful means of revealing and studying magnetic excitations in both natural and artificial frustrated magnets. Depending on the lattice and nature of the frustration, these excitations can often be described as fractionalized quasiparticles possessing an effective magnetic charge. Here, by combining ultrasensitive optical detection of thermodynamic magnetization noise with Monte Carlo simulations, we reveal emergent regimes of magnetic excitations in artificial “tetris ice.” A marked increase of the intrinsic noise at certain applied magnetic fields heralds the spontaneous proliferation of fractionalized excitations, which can diffuse independently, without cost in energy, along specific quasi-1D spin chains in the tetris ice lattice.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Effective field theories for collective excitations of atomic nuclei

Collective modes emerge as the relevant degrees of freedom that govern low-energy excitations of atomic nuclei. These modes—rotations, pairing rotations, and vibrations—are separated in energy from non-collective excitations, making it possible to describe them in the framework of effective field theory. Rotations and pairing rotations are the remnants of Nambu–Goldstone modes from the emergent breaking of rotational symmetry and phase symmetries in finite deformed and finite superfluid nuclei, respectively. The symmetry breaking severely constrains the structure of low-energy Lagrangians and thereby clarifies what is essential and simplifies the description. The approach via effective field theories exposes the essence of nuclear collective excitations and is defined with a breakdown scale in mind. This permits one to make systematic improvements and to estimate and quantify uncertainties. Effective field theories of collective excitations have been used to compute spectra, transition rates, and other matrix elements of interest. In particular, predictions of the nuclear matrix element for neutrinoless double beta decay then come with quantified uncertainties. This review summarizes these results and also compares the approach via effective field theories to well-known models and ab initio computations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗