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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 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Implementation of a Faraday rotation diagnostic at the OMEGA laser facility

Magnetic field measurements in turbulent plasmas are often difficult to perform. Here we show that for ${\geqslant}$ kG magnetic fields, a time-resolved Faraday rotation measurement can be made at the OMEGA laser facility. This diagnostic has been implemented using the Thomson scattering probe beam and the resultant path-integrated magnetic field has been compared with that of proton radiography. As a result, accurate measurement of magnetic fields is essential for satisfying the scientific goals of many current laser–plasma experiments.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2017

Proton imaging of stochastic magnetic fields

Recent laser-plasma experiments report the existence of dynamically significant magnetic fields, whose statistical characterization is essential for a complete understanding of the physical processes these experiments are attempting to investigate. In this paper, we show how a proton-imaging diagnostic can be used to determine a range of relevant magnetic-field statistics, including the magnetic-energy spectrum. To achieve this goal, we explore the properties of an analytic relation between a stochastic magnetic field and the image-flux distribution created upon imaging that field. This ‘Kugland image-flux relation’ was previously derived under simplifying assumptions typically valid in actual proton-imaging set-ups. We conclude that, as with regular electromagnetic fields, features of the beam’s final image-flux distribution often display a universal character determined by a single, field-scale dependent parameter – the contrast parameter $\unicode[STIX]{x1D707}\equiv d_{s}/{\mathcal{M}}l_{B}$ – which quantifies the relative size of the correlation length $l_{B}$ of the stochastic field, proton displacements $d_{s}$ due to magnetic deflections and the image magnification ${\mathcal{M}}$ . For stochastic magnetic fields, we establish the existence of four contrast regimes, under which proton-flux images relate to their parent fields in a qualitatively distinct manner. These are linear, nonlinear injective, caustic and diffusive. The diffusive regime is newly identified and characterized. The nonlinear injective regime is distinguished from the caustic regime in manifesting nonlinear behaviour, but as in the linear regime, the path-integrated magnetic field experienced by the beam can be extracted uniquely. Thus, in the linear and nonlinear injective regimes we show that the magnetic-energy spectrum can be obtained under a further statistical assumption of isotropy. This is not the case in the caustic or diffusive regimes. We discuss complications to the contrast-regime characterization arising for inhomogeneous, multi-scale stochastic fields, which can encompass many contrast regimes, as well as limitations currently placed by experimental capabilities on one’s ability to extract magnetic-field statistics. Furthermore, the results presented in this paper are of consequence in providing a comprehensive description of proton images of stochastic magnetic fields, with applications for improved analysis of proton-flux images.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Importance of Nuclear Quantum Effects on Aqueous Electrolyte Transport under Confinement in Ti 3 C 2 MXenes

Protons display a high chemical activity and strongly affect the charge storage capability in confined interlayer spaces of two-dimensional (2D) materials. As such, an accurate representation of proton dynamics under confinement is important for understanding and predicting charge storage dynamics in these materials. While often ignored in atomistic-scale simulations, nuclear quantum effects (NQEs), e.g., tunneling, can be significant under confinement even at room temperature. Here, using the thermostatted ring polymer molecular dynamics implementation of path integral molecular dynamics (PIMD) in conjunction with the ReaxFF force field, density functional tight binding (DFTB), and NequIP neural network potential simulations, we investigate the role of NQEs on proton and water transport in bulk water and aqueous electrolytes under confinement in Ti 3 C 2 MXenes. Although overall NQEs are relatively small, especially in bulk, we find that they can alter both quantitative values and qualitative trends on both proton transport and water self-diffusion under confinement relative to classical MD predictions. Therefore, our results suggest the need for NQEs to be considered to simulate aqueous systems under confinement for both qualitative and quantitative accuracy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Simple Flux-Side Formulation of State-Resolved Thermal Reaction Rates for Ring-Polymer Surface Hopping

Employing the recently developed isomorphic Hamiltonian framework for including nuclear quantum effects in mixed quantum–classical nonadiabatic dynamics, we present a flux-side formulation of state-resolved thermal reaction rates for ring-polymer surface hopping (iso-RPSH). An appealing aspect of the new approach is that calculation of multiple state-resolved nonadiabatic thermal reaction rates is enabled with only a single free-energy surface calculation, whereas previous nonadiabatic flux-side formulations for surface hopping involve multiple free-energy surface calculations. In conclusion, the method is shown to be robust and straightforwardly implemented, and numerical results reveal that RPSH in the isomorphic Hamiltonian framework leads to better dividing surface independence than alternative RPSH methods due to improved preservation of the path-integral statistics.

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

Modeling Liquid Water by Climbing up Jacob’s Ladder in Density Functional Theory Facilitated by Using Deep Neural Network Potentials

Within the framework of Kohn–Sham density functional theory (DFT), the ability to provide good predictions of water properties by employing a strongly constrained and appropriately normed (SCAN) functional has been extensively demonstrated in recent years. Here, we further advance the modeling of water by building a more accurate model on the fourth rung of Jacob’s ladder with the hybrid functional, SCAN0. In particular, we carry out both classical and Feynman path-integral molecular dynamics calculations of water with the SCAN0 functional and the isobaric–isothermal ensemble. To generate the equilibrated structure of water, a deep neural network potential is trained from the atomic potential energy surface based on ab initio data obtained from SCAN0 DFT calculations. For the electronic properties of water, a separate deep neural network potential is trained by using the Deep Wannier method based on the maximally localized Wannier functions of the equilibrated trajectory at the SCAN0 level. The structural, dynamic, and electric properties of water were analyzed. The hydrogen-bond structures, density, infrared spectra, diffusion coefficients, and dielectric constants of water, in the electronic ground state, are computed by using a large simulation box and long simulation time. For the properties involving electronic excitations, we apply the GW approximation within many-body perturbation theory to calculate the quasiparticle density of states and bandgap of water. Compared to the SCAN functional, mixing exact exchange mitigates the self-interaction error in the meta-generalized-gradient approximation and further softens liquid water toward the experimental direction. For most of the water properties, the SCAN0 functional shows a systematic improvement over the SCAN functional. However, some important discrepancies remain. The H-bond network predicted by the SCAN0 functional is still slightly overstructured compared to the experimental results.

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

Nuclear Quantum Effects on the Electronic Structure of Water and Ice

The electronic properties and optical response of ice and water are intricately shaped by their molecular structure, including the quantum mechanical nature of the hydrogen atoms. Despite numerous previous studies, a comprehensive understanding of the nuclear quantum effects (NQEs) on the electronic structure of water and ice at finite temperatures remains elusive. Here, we utilize molecular simulations that harness efficient machine-learning potentials and many-body perturbation theory to assess how NQEs impact the electronic bands of water and hexagonal ice. By comparing path-integral and classical simulations, we find that NQEs lead to a larger renormalization of the fundamental gap of ice, compared to that of water, ultimately yielding similar bandgaps in the two systems, consistent with experimental estimates. Our calculations suggest that the increased quantum mechanical delocalization of protons in ice, relative to water, is a key factor leading to the enhancement of NQEs on the electronic structure of ice.

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

Quantum Dynamics and Spectroscopy of Ab Initio Liquid Water: The Interplay of Nuclear and Electronic Quantum Effects

Understanding the reactivity and spectroscopy of aqueous solutions at the atomistic level is crucial for the elucidation and design of chemical processes. However, the simulation of these systems requires addressing the formidable challenges of treating the quantum nature of both the electrons and nuclei. Exploiting our recently developed methods that provide acceleration by up to 2 orders of magnitude, we combine path integral simulations with on-the-fly evaluation of the electronic structure at the hybrid density functional theory level to capture the interplay between nuclear quantum effects and the electronic surface. Here we show that this combination provides accurate structure and dynamics, including the full infrared and Raman spectra of liquid water. This allows us to demonstrate and explain the failings of lower-level density functionals for dynamics and vibrational spectroscopy when the nuclei are treated quantum mechanically. Finally, these insights thus provide a foundation for the reliable investigation of spectroscopy and reactivity in aqueous environments.

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

The Quest for Accurate Liquid Water Properties from First Principles

Developing accurate ab initio molecular dynamics (AIMD) models that capture both electronic reorganization and nuclear quantum effects associated with hydrogen bonding is key to quantitative understanding of bulk water and its anomalies, as well as its role as a universal solvent. For condensed phase simulations, AIMD has typically relied on the generalized gradient approximation (GGA) of Density Functional Theory (DFT) as the underlying model chemistry for the potential energy surface, with nuclear quantum effects (NQEs) sometimes modeled by performing classical molecular dynamics simulations at elevated temperatures. Here we show that the properties of liquid water obtained from the meta-GGA B97M-rV functional, when evaluated using accelerated path integral molecular dynamics simulations, displays accuracy comparable to a computationally expensive dispersion corrected hybrid functional, revPBE0-D 3 . We show that the meta-GGA DFT reproduces bulk water properties including radial distribution functions, self-diffusion coefficients, and infrared (IR) spectra with comparable accuracy of a much more expensive hybrid functional. In conclusion, this work demonstrates that the underlying quality of a good DFT functional requires evaluation with quantum nuclei, and that high temperature simulations are a poor proxy for properly treating nuclear quantum effects.

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

On the Interplay of Electronic and Lattice Screening on Exciton Binding in Two-Dimensional Lead Halide Perovskites

We use path integral Monte Carlo to study the energetics of excitons in layered, hybrid organic–inorganic perovskites in order to elucidate the relative contributions of dielectric confinement and electron–phonon coupling. While the dielectric mismatch between polar perovskite layers and nonpolar ligand layers significantly increases the exciton binding energy relative to their three-dimensional bulk crystal counterparts, formation of exciton polarons attenuates this effect. The contribution from polaron formation is found to be a nonmonotonic function of the lead halide layer thickness, which is clarified by a general variational theory. Accounting for both of these effects provides a description of exciton binding energies in good agreement with experimental measurements. By studying isolated layers and stacked layered crystals of various thicknesses, with ligands of varying polarity, we provide a systematic understanding of the excitonic behavior of this class of materials and how to engineer their photophysics.

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

Synthetic Control of Exciton Dynamics in Bioinspired Cofacial Porphyrin Dimers

Understanding how the complex interplay among excitonic interactions, vibronic couplings, and reorganization energy determines coherence-enabled transport mechanisms is a grand challenge with both foundational implications and potential payoffs for energy science. We use a combined experimental and theoretical approach to show how a modest change in structure may be used to modify the exciton delocalization, tune electronic and vibrational coherences, and alter the mechanism of exciton transfer in covalently linked cofacial Zn-porphyrin dimers (meso-beta linked AB m-β and meso-meso linked AA m-m ). While both AB m-β and AA m-m feature zinc porphyrins linked by a 1,2-phenylene bridge, differences in the interporphyrin connectivity set the lateral shift between macrocycles, reducing electronic coupling in AB m-β and resulting in a localized exciton. Pump-probe experiments show that the exciton dynamics is faster by almost an order of magnitude in the strongly coupled AA m-m dimer, and two-dimensional electronic spectroscopy (2DES) identifies a vibronic coherence that is absent in AB m-β . Theoretical studies indicate how the interchromophore interactions in these structures, and their system-bath couplings, influence excitonic delocalization and vibronic coherence-enabled rapid exciton transport dynamics. Real-time path integral calculations reproduce the exciton transfer kinetics observed experimentally and find that the linking-modulated exciton delocalization strongly enhances the contribution of vibronic coherences to the exciton transfer mechanism, and that this coherence accelerates the exciton transfer dynamics. These benchmark molecular design, 2DES, and theoretical studies provide a foundation for directed explorations of nonclassical effects on exciton dynamics in multiporphyrin assemblies.

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

Electron affinity of liquid water

Understanding redox and photochemical reactions in aqueous environments requires a precise knowledge of the ionization potential and electron affinity of liquid water. The former has been measured, but not the latter. We predict the electron affinity of liquid water and of its surface from first principles, coupling path-integral molecular dynamics with ab initio potentials, and many-body perturbation theory. Our results for the surface (0.8 eV) agree well with recent pump-probe spectroscopy measurements on amorphous ice. Those for the bulk (0.1-0.3 eV) differ from several estimates adopted in the literature, which we critically revisit. We show that the ionization potential of the bulk and surface are almost identical; instead their electron affinities differ substantially, with the conduction band edge of the surface much deeper in energy than that of the bulk. We also discuss the significant impact of nuclear quantum effects on the fundamental gap and band edges of the liquid.

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

Neutron scattering and neural-network quantum molecular dynamics investigation of the vibrations of ammonia along the solid-to-liquid transition

Abstract Vibrational spectroscopy allows us to understand complex physical and chemical interactions of molecular crystals and liquids such as ammonia, which has recently emerged as a strong hydrogen fuel candidate to support a sustainable society. We report inelastic neutron scattering measurement of vibrational properties of ammonia along the solid-to-liquid phase transition with high enough resolution for direct comparisons to ab-initio simulations. Theoretical analysis reveals the essential role of nuclear quantum effects (NQEs) for correctly describing the intermolecular spectrum as well as high energy intramolecular N-H stretching modes. This is achieved by training neural network models using ab-initio path-integral molecular dynamics (PIMD) simulations, thereby encompassing large spatiotemporal trajectories required to resolve low energy dynamics while retaining NQEs. Our results not only establish the role of NQEs in ammonia but also provide general computational frameworks to study complex molecular systems with NQEs.

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

Unraveling electronic correlations in warm dense quantum plasmas

The study of matter at extreme densities and temperatures has emerged as a highly active frontier at the interface of plasma physics, material science and quantum chemistry with relevance for planetary modeling and inertial confinement fusion. A particular feature of such warm dense matter is the complex interplay of Coulomb interactions, quantum effects, and thermal excitations, making its rigorous theoretical description challenging. Here, we demonstrate how ab initio path integral Monte Carlo simulations allow us to unravel this intricate interplay for the example of strongly compressed beryllium, focusing on two X-ray Thomson scattering data sets obtained at the National Ignition Facility. We find excellent agreement between simulation and experiment with a very high level of consistency between independent observations without the need for any empirical input parameters. Our results call into question previously used chemical models, with important implications for the interpretation of scattering experiments and radiation hydrodynamics simulations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Nuclear quantum effects in molecular liquids across chemical space

Abstract Nuclear quantum effects (NQEs) influence many physical and chemical phenomena, particularly those involving light atoms or occurring at low temperatures. However, their impact has been carefully quantified in few systems-like water-and is rarely considered more broadly. Here we use path-integral molecular dynamics to systematically investigate NQEs on thermophysical properties of 92 organic liquids at ambient conditions. Depending on chemical constitution, we find substantial impact across thermal expansivity, compressibility, dielectric constant, enthalpy of vaporization, and notably molar volume, which shows consistent, positive quantum-classical differences up to 5%; similar, less pronounced trends manifest as isotope effects from deuteration. Using data-driven analysis, we identify three features-molar mass, classical hydrogen density, and classical thermal expansivity-that accurately predict NQEs and facilitate understanding of how characteristics like branching and heteroatom content influence behavior. This work highlights the broad relevance of NQEs in molecular liquids, while also providing a conceptual and practical framework to anticipate their impact.

Science & Technology - Other Topics↗
DOE OSTI2024

Deuteration removes quantum dipolar defects from KDP crystals

Abstract Dielectric properties of the hydrogen-bonded ferroelectric crystal KH 2 PO 4 (KDP) differ significantly from those of KD 2 PO 4 (DKDP). It is well established that deuteration affects the interplay of hydrogen-bond switches and heavy ion displacements that underlie the emergence of macroscopic polarization, but a detailed microscopic model is missing. We show that all-atom path integral molecular dynamics simulations can predict the isotope effects, revealing the microscopic mechanism that differentiates KDP and DKDP. Proton tunneling generates phosphate configurations that do not contribute to the polarization. At low temperatures, these quantum dipolar defects are substantial in KDP but negligible in DKDP. These intrinsic defects explain why KDP has lower spontaneous polarization and transition entropy than DKDP. The prominent role of quantum fluctuations in KDP is related to the unusual strength of the hydrogen bonds and should be equally important in other crystals of the KDP family, which exhibit similar isotope effects.

Yang, Bingjia (ORCID:0000000340749553)↗
DOE OSTI2026

Enhancing the efficiency of time-dependent density functional theory calculations of dynamic response properties

X-ray Thomson scattering (XRTS) constitutes an essential technique for diagnosing material properties under extreme conditions, such as high pressures and intense laser heating. Time-dependent density functional theory (TDDFT) is one of the most accurate available ab initio methods for modeling XRTS spectra, as well as a host of other dynamic material properties. However, strong thermal excitations, along with the need to account for variations in temperature and density as well as the finite size of the detector significantly increase the computational cost of TDDFT simulations compared to ambient conditions. In this work, we present a broadly applicable method for optimizing and enhancing the efficiency of TDDFT calculations. Our approach is based on a one-to-one mapping between the dynamic structure factor and the imaginary time density–density correlation function, which naturally emerges in Feynman’s path integral formulation of quantum many-body theory. Specifically, we combine rigorous convergence tests in the imaginary time domain with a constraints-based attenuation of narrow-band fluctuations to improve the efficiency of TDDFT modeling without the introduction of any significant bias. As a result, we can report a speed-up by up to an order of magnitude, thus substantially reducing the burden of computational cost required for XRTS analysis.

Moldabekov, Zhandos A. [Helmholtz-Zentrum Dresden-↗
DOE OSTI2020

Developing new and understanding old approximations in TDDFT

When a system has evolved far from a ground-state, the adiabatic approximations commonly used in time-dependent density functional theory calculations completely fail in some applications, while giving qualitatively good predictions in others, and sometimes even quantitative predictions. It is not clearly understood why this is so, and developing practical approximations going beyond the adiabatic approximation remains a challenge. This paper explores three different lines of investigation. First, an expression for the exact time-dependent exchange–correlation potential suggests that the accuracy of an adiabatic approximation is intimately related to the deviation between the natural orbital occupation numbers of the physical system and those of the Kohn–Sham system, and we explore this on some exactly-solvable model systems. The exact expression further suggests a path to go beyond the adiabatic approximations, and in the second part we discuss a newly proposed class of memory-dependent approximations developed in this way. Finally, we derive a new expression for the exact exchange–correlation potential from a coupling-constant path integration.

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

Simultaneous streak and frame interferometry for electron density measurements of laser produced plasmas

A system of two collinear probe beams with different wavelengths and pulse durations was used to capture simultaneously snapshot interferograms and streaked interferograms of laser produced plasmas. The snapshots measured the two dimensional, path-integrated, electron density on a charge-coupled device while the radial temporal evolution of a one dimensional plasma slice was recorded by a streak camera. This dual-probe combination allowed us to select plasmas that were uniform and axisymmetric along the laser direction suitable for retrieving the continuous evolution of the radial electron density of homogeneous plasmas. Demonstration of this double probe system was done by measuring rapidly evolving plasmas on time scales less than 1 ns produced by the interaction of femtosecond, high intensity, laser pulses with argon gas clusters. Experiments aimed at studying homogeneous plasmas from high intensity laser-gas or laser-cluster interaction could benefit from the use of this probing scheme.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗