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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 703 records · Page 39
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Analysis of Fourth-, Fifth-, and Infinite-Order Triple Excitations in Unitary Coupled Cluster Theory

Here, in this work, we introduce a perturbative correction to the unitary coupled cluster method with single and double excitations (UCCSD) that incorporates the effects of missing triple excitations through fifth-order in many-body perturbation theory (MBPT). Referred to as UCCSD[T-5], this method is benchmarked alongside the previously developed UCCSD[T] to lend insight into the behavior of perturbative triples corrections relative to UCCSDT, which inherently provides an infinite-order treatment of triple excitations, as well as full configuration interaction (FCI). Two key findings emerge from this analysis. First, UCCSD[T] consistently yields ground-state energies in closest agreement with FCI, outperforming both UCCSD[T-5] and UCCSDT. Second, UCCSD[T-5] largely emulates the behavior of UCCSDT, suggesting a close relationship between fifth- and infinite-order triple-excitation contributions. Given the growing interest in UCC ansätze for quantum computing and the limitations of current quantum hardware, these results highlight the potential of classically computed perturbative corrections within UCC theory to capture triple-excitation effects without the additional quantum resources required by the UCCSDT ansatz.

Windom, Zachary W. [Oak Ridge National Laboratory ↗
DOE OSTI2023

Curing the Divergence in Time-Dependent Density Functional Quadratic Response Theory

While time-dependent density functional theory has emerged as a method of choice for computing electronic spectra and response of molecules and materials, its reliability is hindered by the adiabatic approximation that is commonly made. In this work, we address one problematic aspect that arises from this approximation: an incorrect pole structure in the quadratic response function, leading to unphysical divergences in excited state-to-state transition probabilities and hyperpolarizabilties. We find the form of the exact quadratic response kernel and derive a practical and accurate approximation that cures the divergence. Here, we demonstrate our results on excited state-to-state transition probabilities of a model system and of the LiH molecule.

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

Coupled order parameters and photoinduced domain walls in the charge density wave of (TaSe 4 ) 2 I

The charge density wave in (TaSe 4 ) 2 I has drawn much attention recently as a controversial candidate for an axion insulator where the CDW breaks the chiral symmetry of the Weyl semimetal. Here we use ultrafast x-ray scattering to study the collective modes of this CDW. By measuring several diffraction peaks we find that the order parameter involves coupled optical and acoustic modes. For strong near-infrared excitation, the dynamics of the x-ray diffraction show evidence of photoinduced inversion of both components of the CDW order parameter, and associated domain walls. These results demonstrate the potential of ultrafast methods to induce topological defects through highly nonequilibrium dynamics. In (TaSe 4 ) 2 I these defects should lead to exotic electronic states due to the nontrivial topology of the band structure.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Light–matter interaction of a molecule in a dissipative cavity from first principles

Cavity-mediated light–matter coupling can dramatically alter opto-electronic and physico-chemical properties of a molecule. Ab initio theoretical predictions of these systems need to combine non-perturbative, many-body electronic structure theory-based methods with cavity quantum electrodynamics and theories of open-quantum systems. Here, we generalize quantum-electrodynamical density functional theory to account for dissipative dynamics of the cavity and describe coupled cavity–single molecule interactions in the weak-to-strong-coupling regimes. Specifically, to establish this generalized technique, we study excited-state dynamics and spectral responses of benzene and toluene under weak-to-strong light–matter coupling. By tuning the coupling, we achieve cavity-mediated energy transfer between electronically excited states. This generalized ab initio quantum-electrodynamical density functional theory treatment can be naturally extended to describe cavity-mediated interactions in arbitrary electromagnetic environments, accessing correlated light–matter observables and thereby closing the gap between electronic structure theory, quantum optics, and nanophotonics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1974

Temperature dependence of vibrational relaxation in the HF, DF, HF-CO2, and DF-CO2 systems

The laser excited fluorescence method has been employed to determine rate constants for V to V, R and V to R, T relaxation HF (nu = 1) and DF(nu = 1) by CO2 over the temperature range from 295 to 670 K. The self-deactivation rates for HF(nu = 1) and DF(nu = 1) by ground state molecules and the rate of V to V, R transfer from HF(nu = 1) and DF(nu = 1) to the CO2 (00/0/1) state exhibit a marked decrease with increasing temperature. The results provide additional evidence for the conversion of the large vibrational energy defects of the present systems into rotational motion of the hydrogen halide under the influence of a sizable attractive intermolecular potential well.

Lucht, R. A.↗
DOE OSTI2025

Floquet Engineering of Interactions and Entanglement in Periodically Driven Rydberg Chains

Neutral atom arrays driven into Rydberg states constitute a promising approach for realizing programmable quantum systems. Enabled by strong interactions associated with Rydberg blockade, they allow for simulation of complex spin models and quantum dynamics. We introduce a new Floquet engineering technique for systems in the blockade regime that provides control over novel forms of interactions and entanglement dynamics in such systems. Our approach is based on time-dependent control of Rydberg laser detuning and leverages perturbations around periodic many-body trajectories as resources for operator spreading. These time-evolved operators are utilized as a basis for engineering interactions in the effective Hamiltonian describing the stroboscopic evolution. As an example, we show how our method can be used to engineer strong spin exchange, consistent with the blockade, in a one-dimensional chain, enabling the exploration of gapless Luttinger liquid phases. In addition, we demonstrate that combining gapless excitations with Rydberg blockade can lead to dynamic generation of large-scale multipartite entanglement. Experimental feasibility and possible generalizations are discussed.

Floquet systems↗
DOE OSTI2025

Efficient up-conversion in CsPbBr 3 nanocrystals via phonon-driven exciton-polaron formation

Lead halide perovskite nanocrystals demonstrate efficient up-conversion, although the precise mechanism remains a subject of active research. This study utilizes steady-state and time-resolved spectroscopy methods to unravel the mechanism driving the up-conversion process in CsPbBr 3 nanocrystals. Employing above- and below-gap photoluminescence measurements, we extract a distinct phonon mode with an energy of ~7 meV and identify the Pb-Br-Pb bending mode as the phonon involved in the up-conversion process. This result was corroborated by Raman spectroscopy. We confirm an up-conversion efficiency reaching up to 75%. Transient absorption measurements under conditions of sub-gap excitation also unexpectedly reveal coherent phonons for the subset of nanocrystals undergoing up-conversion. This coherence implies that the up-conversion and subsequent relaxation is accompanied by a synchronized and phased lattice motion. This study reveals that efficient up-conversion in CsPbBr 3 nanocrystals is powered by a unique interplay between the soft lattice structure, phonons, and excited states dynamics.

Anti-Stokes Photoluminescence↗
NASA NTRS1993

Nonlinear vibrations of thin arbitrarily laminated composite plates subjected to harmonic excitations using DKT elements

A finite element formulation is presented for determining the large-amplitude free and steady-state forced vibration response of arbitrarily laminated anisotropic composite thin plates using the Discrete Kirchhoff Theory (DKT) triangular elements. The nonlinear stiffness and harmonic force matrices of an arbitrarily laminated composite triangular plate element are developed for nonlinear free and forced vibration analyses. The linearized updated-mode method with nonlinear time function approximation is employed for the solution of the system nonlinear eigenvalue equations. The amplitude-frequency relations for convergence with gridwork refinement, triangular plates, different boundary conditions, lamination angles, number of plies, and uniform versus concentrated loads are presented.

Chiang, C. K.↗
DOE OSTI2024

Homological Invariants of Pauli Stabilizer Codes

Abstract We study translationally invariant Pauli stabilizer codes with qudits of arbitrary, not necessarily uniform, dimensions. Using homological methods, we define a series of invariants called charge modules. We describe their properties and physical meaning. The most complete results are obtained for codes whose charge modules have Krull dimension zero. This condition is interpreted as mobility of excitations. We show that it is always satisfied for translation invariant 2D codes with unique ground state in infinite volume, which was previously known only in the case of uniform, prime qudit dimension. For codes all of whose excitations are mobile we construct a p-dimensional excitation and a $$(D-p-1)$$ ( D - p - 1 ) -form symmetry for every element of thep-th charge module. Moreover, we define a braiding pairing between charge modules in complementary degrees. We discuss examples which illustrate how charge modules and braiding can be computed in practice.

Physics↗
DOE OSTI2025

Lanczos Algorithm, the Transfer Matrix, and the Signal-to-Noise Problem

This Letter introduces a method for determining the energy spectrum of lattice quantum chromodynamics by applying the Lanczos algorithm to the transfer matrix and using a bootstrap generalization of the Cullum-Willoughby method to filter out spurious eigenvalues. Proof-of-principle analyses of the simple harmonic oscillator and the lattice quantum chromodynamics proton mass demonstrate that this method provides faster ground-state convergence than the “effective mass,” which is related to the power-iteration algorithm. Lanczos provides more accurate energy estimates than multistate fits to correlation functions with small imaginary times while achieving comparable statistical precision. Two-sided error bounds are computed for Lanczos results and guarantee that excited-state effects cannot shift Lanczos results far outside their statistical uncertainties.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS1971

Molecular collisions. XVI.

The comparison indicates that the present version of the GPS method overestimates the rotational excitation and underestimates the de-excitation, while maintaining the total inelasticity at approximately the correct exact classical trajectory value. An approximate ?quantization' of the classical results leads to an estimate of the quantal cross sections corresponding to changes by plus or minus 2, 4, and 6 from an initial rotor quantum state 10. It is found that most of the total inelastic cross section arises from the first-order-allowed transitions.

Pattengill, M. D.↗
NASA NTRS1973

Nonlinear transient analysis of multi-mass flexible rotors - theory and applications

The equations of motion necessary to compute the transient response of multi-mass flexible rotors are formulated to include unbalance, rotor acceleration, and flexible damped nonlinear bearing stations. A method of calculating the unbalance response of flexible rotors from a modified Myklestad-Prohl technique is discussed in connection with the method of solution for the transient response. Several special cases of simplified rotor-bearing systems are presented and analyzed for steady-state response, stability, and transient behavior. These simplified rotor models produce extensive design information necessary to insure stable performance to elastic mounted rotor-bearing systems under varying levels and forms of excitation. The nonlinear journal bearing force expressions derived from the short bearing approximation are utilized in the study of the stability and transient response of the floating bush squeeze damper support system. Both rigid and flexible rotor models are studied, and results indicate that the stability of flexible rotors supported by journal bearings can be greatly improved by the use of squeeze damper supports. Results from linearized stability studies of flexible rotors indicate that a tuned support system can greatly improve the performance of the units from the standpoint of unbalanced response and impact loading. Extensive stability and design charts may be readily produced for given rotor specifications by the computer codes presented in this analysis.

Kirk, R. G.↗
NASA NTRS1976

Monte Carlo calculations of diatomic molecule gas flows including rotational mode excitation

The direct simulation Monte Carlo method was used to solve the Boltzmann equation for flows of an internally excited nonequilibrium gas, namely, of rotationally excited homonuclear diatomic nitrogen. The semi-classical transition probability model of Itikawa was investigated for its ability to simulate flow fields far from equilibrium. The behavior of diatomic nitrogen was examined for several different nonequilibrium initial states that are subjected to uniform mean flow without boundary interactions. A sample of 1000 model molecules was observed as the gas relaxed to a steady state starting from three specified initial states. The initial states considered are: (1) complete equilibrium, (2) nonequilibrium, equipartition (all rotational energy states are assigned the mean energy level obtained at equilibrium with a Boltzmann distribution at the translational temperature), and (3) nonequipartition (the mean rotational energy is different from the equilibrium mean value with respect to the translational energy states). In all cases investigated the present model satisfactorily simulated the principal features of the relaxation effects in nonequilibrium flow of diatomic molecules.

Yoshikawa, K. K.↗
DOE OSTI2023

Tracking Photochemical and Photophysical Processes for Solar Energy Conversion Via Multidimensional Visible and Vibrational Spectroscopic Methods

This project was motivated by an overarching goal to elucidate the mechanism of energy and electron transfer that governs the efficient charge separation in photosystem I (PSI) complexes. PSI is a natural light harvesting complex that drives oxygenic photosynthesis in plants, algae, and cyanobacteria. It uses ~300 tightly packed chlorophylls (Chls) to absorb photons, transfer the excitation energy to the reaction center (RC), and generate a charge separated state with near unity quantum efficiency (QE). A better understanding of the mechanism of energy transfer and charge separation in PSI is required for understanding the high QE of natural light harvesting complexes, and it could lead to the further development of artificial photosynthetic systems for solar energy conversion. We applied two-dimensional electronic spectroscopy (2DES) to different cyanobacterial photosystem I complexes to map energy transfer pathways to gain insight into the efficient light harvesting of PSI. We interpreted the 2DES spectra through a global analysis procedure, finding two ultrafast equilibration processes involving red-shifted Chl states. The analysis procedure is general and can be readily applied to other natural and artificial light harvesting systems. In addition to investigating PSI complexes, we also performed measurements on model systems to establish general data analysis procedures for interpreting 2D spectra.

14 SOLAR ENERGY↗
DOE OSTI2026

Ultrafast nano-imaging and nano-spectroscopy

Ultrafast pump–probe nano-imaging combines scanning probe-based optical near-field microscopy with ultrafast spectroscopy to enable imaging with deep sub-wavelength spatial resolution, femtosecond temporal resolution and simultaneous spectral resolution. Ultrafast nano-imaging has gained increased attention for its ability to provide far-from-equilibrium excitation and excited-state contrast. With coherent and nonlinear probing, coupled electron, spin and lattice dynamics on elementary timescale and length scale can be resolved. Through nano-movies, ultrafast nano-imaging visualizes correlated quantum dynamics underlying the properties of solid-state materials, semiconductors, molecular electronic, photonic, photovoltaic and other functional materials. With nanometre spatial resolution, this method probes elementary dynamic processes across multiple length scales that are otherwise obscured in conventional ultrafast spectroscopy in which heterogeneities are spatially averaged. Furthermore, this Primer describes the theoretical background and experimental implementation of ultrafast nano-imaging; signal interpretation and modelling; representative examples and a perspective for the future development of the field.

Microscopy↗
DOE OSTI2022

Characterizing coherences in chemical dynamics with attosecond time-resolved x-ray absorption spectroscopy

Coherence can drive wave-like motion of electrons and nuclei in photoexcited systems, which can yield fast and efficient ways to exert materials’ functionalities beyond the thermodynamic limit. The search for coherent phenomena has been a central topic in chemical physics although their direct characterization is often elusive. Here, we highlight recent advances in time-resolved x-ray absorption spectroscopy (tr-XAS) to investigate coherent phenomena, especially those that utilize the eminent light source of isolated attosecond pulses. The unparalleled time and state sensitivities of tr-XAS in tandem with the unique element specificity render the method suitable to study valence electronic dynamics in a wide variety of materials. The latest studies have demonstrated the capabilities of tr-XAS to characterize coupled electronic–structural coherence in small molecules and coherent light–matter interactions of core-excited excitons in solids. Furthermore, we address current opportunities and challenges in the exploration of coherent phenomena, with potential applications for energy- and bio-related systems, potential crossings, strongly driven solids, and quantum materials, and so with the ongoing developments in both theory and light sources, tr-XAS holds great promise for revealing the role of coherences in chemical dynamics.

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

GDB-9-Ex_TD-DFT-PBE0: Dataset containing Time Dependent Density Functional Theory (TDDFT) calculations for organic molecules of the GDB-9-Ex dataset.

This dataset contains data-intensive quantum chemical electronic structure calculations for 96,766 organic molecules of the GDB-9-Ex dataset. Calculations were performed using the Time Dependent Density Functional Theory (TDDFT) first principles method using the ORCA software. It provides UV-vis spectra calculations of molecules with a high level of accuracy. The optical spectra behavior was collected based on the optimized molecular geometries in the DFTB method with 3ob parameters. All calculations utilized the def2-TZVP basis sets with the auxiliary def2/J and def2-TZVP/C basis sets. The time-dependent density-functional theory (TDDFT) approach with the PBE0 exchange-correlation functional and ORCAs default integration grid was employed. For the excitation energy calculations, the lowest 50 excitation states were calculated.

AI dataset↗
NASA NTRS1987

State-space formulation of multi-shaker modal analysis

As modal testing techniques have improved in recent years, the demands placed on the accuracy of modal test results have increased. This paper describes a new multi-input, multi-output modal parameter estimation algorithm suitable for the identification of reduced-order models of structures. The method described is a frequency-domain method based on excitation and response spectra. The principal features of the algorithm are: (1) applicability to general linear, time-invariant systems, (2) direct use of multiple input and multiple response data, (3) identification of reduced-order models with minimum user interaction through the use of two automatic model-reduction techniques, (4) identification of a consistent set of modal parameters through the use of numerically stable least-squares techniques, and (5) complete user documentation.

Craig, Roy R., Jr.↗