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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 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Origin of core-to-core x-ray emission spectroscopy sensitivity to structural dynamics

Recently, coherent structural dynamics in the excited state of an iron photosensitizer was observed through oscillations in the intensity of Kα x-ray emission spectroscopy (XES). Understanding the origin of the unexpected sensitivity of core-to-core transitions to structural dynamics is important for further development of femtosecond time-resolved XES methods and, we believe, generally necessary for interpretation of XES signals from highly non-equilibrium structures that are ubiquitous in photophysics and photochemistry. Here, we use multiconfigurational wavefunction calculations combined with atomic theory to analyze the emission process in detail. The sensitivity of core-to-core transitions to structural dynamics is due to a shift of the minimum energy metal–ligand bond distance between 1s and 2p core-hole states. A key effect is the additional contraction of the non-bonding 3s and 3p orbitals in 1s core-hole states, which decreases electron– electron repulsion and increases overlap in the metal–ligand bonds. The effect is believed to be general and especially pronounced for systems with strong bonds. The important role of 3s and 3p orbitals is consistent with the analysis of radial charge and spin densities and can be connected to the negative chemical shift observed for many transition metal complexes. The XES sensitivity to structural dynamics can be optimized by tuning the emission energy spectrometer, with oscillations up to ±4% of the maximum intensity for the current system. The theoretical predictions can be used to design experiments that separate electronic and nuclear degrees of freedom in ultrafast excited state dynamics.

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

Understanding grain boundary segregation under irradiation: A mesoscale modeling study

Grain boundaries (GBs) are an important component in the design of irradiation resistant materials as they play a crucial role as point defect sinks for non-equilibrium vacancies and self-interstitials. However, in the presence of sustained point defect fluxes, the coupled transport of atomic components with inherently different diffusivities often leads to radiation-induced segregation (RIS), with undesired effects on properties such as intergranular corrosion and stress-assisted cracking. In this talk, we investigate the fundamental mechanisms leading to GB segregation in BCC FeCr-based alloys using multiscale modeling and experiments. A phase-field model is employed to account for both thermodynamic and kinetic segregation mechanisms. The full Onsager transport matrix is derived using kinetic Monte Carlo, molecular dynamics, and kinetic cluster expansion (KineCluE) calculations. The thermodynamics of GB segregation is described via an atomic density-based modification to the CALPHAD free energy. The modeling predictions are then compared against segregation data from atom probe characterization for various temperatures, compositions, and neutron irradiation conditions. We will conclude by discussing the utility of the multiscale modeling approach to shed light on the fundamental mechanisms leading to solute-GB interaction.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Partially polaron-transformed quantum master equation for exciton and charge transport dynamics

Polaron-transformed quantum master equation (PQME) offers a unified framework to describe the dynamics of quantum systems in both limits of weak and strong couplings to environmental degrees of freedom. Thus, the PQME serves as an efficient method to describe charge and exciton transfer/transport dynamics for a broad range of parameters in condensed or complex environments. However, in some cases, the polaron transformation (PT) being employed in the formulation invokes an over-relaxation of slow modes and results in premature suppression of important coherence terms. A formal framework to address this issue is developed in the present work by employing a partial PT that has smaller weights for low frequency bath modes. In this work, it is shown that a closed form expression of a second order time-local PQME including all the inhomogeneous terms can be derived for a general form of partial PT, although more complicated than that for the full PT. All the expressions needed for numerical calculation are derived in detail. Applications to a model of a two-level system coupled to a bath of harmonic oscillators, with test calculations focused on those due to homogeneous relaxation terms, demonstrate the feasibility and the utility of the present approach.

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

Light-induced electron dynamics of molecules in cavities: comparison of model Hamiltonians

The rapidly expanding field of polaritonic chemistry requires accurate theoretical simulations to understand new phenomena at the atomic scale. Computing the optoelectronic properties of molecules using established electronic structure methods is a careful balance of accuracy and computational expense, and expanding these methods to quantum electrodynamics to describe coupled cavity-molecule systems is an active topic of development. Key to these methods are the Hamiltonian operators representing the photon cavity modes. The recently introduced quantum electrodynamics time-dependent configuration interaction (QED-TDCI) method allows for the combination of electron dynamics simulations with quantum electrodynamics, enabling the simulation of time-dependent optoelectronic properties of cavity-molecule systems. Using this method, a comparison of two many-state QED Hamiltonians—the Pauli-Fierz and quantum Rabi model Hamiltonians—is presented, with a particular focus on time-dependent properties in applied electric fields.

Peyton, Benjamin G. (ORCID:0000000163190751)↗
DOE OSTI2020

Fast and Universal Kohn-Sham Density Functional Theory Algorithm for Warm Dense Matter to Hot Dense Plasma

Understanding many processes, e.g., fusion experiments, planetary interiors, and dwarf stars, depends strongly on microscopic physics modeling of warm dense matter and hot dense plasma. This complex state of matter consists of a transient mixture of degenerate and nearly free electrons, molecules, and ions. This regime challenges both experiment and analytical modeling, necessitating predictive ab initio atomistic computation, typically based on quantum mechanical Kohn-Sham density functional theory (KS-DFT). However, cubic computational scaling with temperature and system size prohibits the use of DFT through much of the warm dense matter regime. A recently developed stochastic approach to KS-DFT can be used at high temperatures, with the exact same accuracy as the deterministic approach, but the stochastic error can converge slowly and it remains expensive for intermediate temperatures (< 50 eV). Here we have developed a universal mixed stochastic-deterministic algorithm for DFT at any temperature. This approach leverages the physics of KS-DFT to seamlessly integrate the best aspects of these different approaches. We demonstrate that this method significantly accelerated self-consistent field calculations for temperatures from 3 to 50 eV, while producing stable molecular dynamics and accurate diffusion coefficients.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Ultrafast studies of elusive chemical reactions in the gas phase

The chemical composition of the interstellar medium and planetary atmospheres is constantly in flux as atoms and molecules collide and interact with high-energy particles such as electrons, protons, and photons. These transformative processes ultimately lead to the coalescence of molecules and eventually the birth of stars. Our understanding of these chemical ecosystems relies on models that synthesize data from gas-phase experiments, providing insights into reaction cross sections. This Review examines efforts to delve into the fundamental bond-forming and bond-breaking dynamics that occur during bimolecular and electron-initiated reactions. Furthermore, these experiments involve clever approaches to establish a time reference and the collision geometry necessary for tracking atomic motion with femtosecond time resolution. Findings from these efforts enhance present models and improve predictions for molecule-molecule and electron-molecule collisions.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

An ab initio molecular dynamics investigation of the thermophysical properties of molten NaCl-MgCl 2

Molten salts have many applications in the nuclear and solar energy industries for thermal storage and heat transfer applications. However, there is a knowledge gap in molten salt thermophysical properties which hinders the technical readiness level of molten salt applications, especially in the nuclear industry. A common method of investigating new materials is through ab initio Molecular Dynamics (AIMD) simulations which is an effective tool to investigate structural and thermophysical properties at realistic temperatures. NaCl-MgCl 2 is an inexpensive salt that is a good candidate for use as a heat transfer medium in solar power applications or in the secondary loop of a nuclear reactor. In this article, the thermophysical properties of NaCl-MgCl 2 are computed via AIMD calculations to supplement the limited experimental studies in the literature. Here a wide range of compositions and temperatures for the pseudo-binary NaCl-MgCl 2 were used to calculate the density, heat capacity, compressibility, enthalpy of mixing, and volumetric thermal expansion coefficient. AIMD is shown to accurately model the densities of molten NaCl-MgCl 2 as there is good agreement with the available literature. This work observed a transition to a monotonic increase of the density with respect to MgCl 2 composition occurring above 1100 K. The heat capacity values increase uniformly with respect to concentration of MgCl 2 at a rate of 2.85 J/mol-K per 10 mol% of MgCl 2 . Select thermophysical properties are fit to a Redlich-Kister expansion for utilization in multiphysics simulations.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Direct Ab Initio Simulation of the Synthesis of BaZrO 3 and the Microstructure Impacts on Proton Transport

Controlling and predicting the processing-structure-performance relationship in functional materials is a grand challenge in materials science, with important implications for a wide range of emerging applications; a high fidelity understanding of the performance impact of microstructures formed under synthesis conditions is required to develop advanced materials, such as solid-state fuel cells and electrolyzers. Using the ceramic BaZrO 3 as a case study, we directly simulate the synthesis and investigate how proton transport is dictated by microstructures. We develop a framework that couples density functional theory (DFT), machine-learning interatomic potential (MLIP) driven molecular dynamics, and grand canonical Monte Carlo to perform large-scale, microstructure-resolved, atomistic simulations of proton transport in experimentally representative polycrystalline structures. Our fully ab initio approach, using a MLIP as a proxy for DFT, allows us to quantify the competition between two distinct diffusion mechanisms: one associated with grain-boundary regions and another within grains. When the impacts of grain boundaries are taken into account, proton transport exhibits substantial deviation from the bulk oxide limit. This addresses long-standing discrepancies between theory and experiments. Our integrated approach provides atomistic insight into microstructure-dependent proton pathways in BaZrO 3 and establishes a general protocol for predicting processing-structure-performance relationships.

organic↗
DOE OSTI2020

Silica nanocluster binding rate coefficients from molecular dynamics trajectory calculations

Oxide nanoparticle growth from vapor phase precursors occurs in high temperature aerosol reactors first via the formation of nanoclusters, which are nanometer-scale condensed-phase species composed of 10 1 -10 2 atoms. The binding rate for nanoclusters, defined as the rate at which two nanoclusters collide with and stick to one another, is hence of interest in predicting nanoparticle size distribution functions in an aerosol. We have utilized molecular dynamics (MD) trajectory calculations to determine the homogeneous (equal-sized) and heterogeneous (disparate-sized) binding rate coefficients of SiO2 (silica) nanoclusters composed of 18, 144, and 333 atoms. MD trajectory calculations incorporated all-atom models of nanoclusters using a combined Born–Huggins–Mayer-Lennard-Jones potential model, which accounts for both short range interactions and electrostatic interactions. MD calculations were utilized to determine the binding probability as a function of both initial relative velocity and impact parameter; integration of the binding probability across impact parameter and relative velocity space yields the binding rate coefficient. MD trajectory calculations reveal that the most common type of encounters between nanoclusters leading to binding are grazing collisions, i.e. instances where collision would not occur without induced dipole potential influences. The resulting binding rate coefficients are found to be extremely weakly dependent on system temperature, which is in contrast to the use of rate coefficient models which are the product of a hard-sphere collision rate coefficient and a constant enhancement factor (leading to a rate coefficient proportional to the square root of temperature). Enhancement factors defined from MD trajectory calculations fall in the range of 3–9 as system temperature decreases from 1500 K to 300 K. Furthermore, such large values suggest that potential interactions need to be considered when modeling oxide nanocluster growth in the gas phase.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Unraveling spin entanglement using quantum gates with scanning tunneling microscopy-driven electron spin resonance

Quantum entanglement is a fundamental resource for quantum information processing, and its controlled generation and detection remain key challenges in scalable quantum architectures. Here, we numerically demonstrate the deterministic generation of entangled spin states in a solid-state platform by implementing quantum gates via electron spin resonance combined with scanning tunneling microscopy (ESR-STM). Using two titanium atoms on a MgO/Ag(100) substrate as a model, we construct a two-qubit system whose dynamics are coherently manipulated through tailored microwave pulse sequences. We generate Bell states by implementing a Hadamard gate followed by a controlled-NOT gate, and evaluate its fidelity and concurrence using the quantum-master equation-based code TimeESR. Our results demonstrate that ESR-STM can create entangled states with significant fidelity. This study paves the way for the realization of atom-based quantum circuits and highlights ESR-STM as a powerful tool for probing and engineering entangled states on surfaces.

Switzer, Eric D. [Donostia International Physics C↗
DOE OSTI2022

Plasma Mirrors For High Power Lasers: A new approach for high repetition rates combined with realistic PIC simulations

We describe a research program to develop high quality plasma mirrors for use with high repetition rate, high power laser facilities to greatly facilitate experiments in high energy density physics, particularly when using solid density targets. A system delivering ultrathin, free standing liquid crystal films that could handle PW class laser pulses was developed that preserved the laser beam image quality and improved pulse contrast by over two orders of magnitude. The pulse contrast improvement was measured using a high dynamic range cross-correlation. The system operated at a repetition rate of several PMs formed in situ per minute. Extension to 1 Hz repetition rates should be possible. As a practical application, a PM system was used to separate laser accelerated electrons from the ultrashort pulse drive laser so that the electron beam emittance could be directly measured. The 20 nm thick PMs did not contribute significantly to emittance degradation. It was also demonstrated that the films could operate in the difficult plasma and laser environment present for GeV laser based electron acceleration. PM operation is still not well understood and much work with PMs is done empirically. Accordingly, we also demonstrated a particle-in-cell based simulation technique that would model PM operation, tracking the PM operation from cold, neutral atoms to a hot dense plasma by accounting for multiphoton ionization, plasma collisionality, and the dynamically changing index of refraction. Simulations in 3D were compared to a 2D based approach that was comparable. Finally, we developed a simpler model that can predict the intensity at which a plasma mirror will have its peak reflectivity.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Modified Lucas-Washburn theory for fluid filling in nanotubes

Ultrafast water transport in carbon nanotubes (CNTs) has drawn a great deal of attention in a number of applications, such as water desalination, power generation, and biomolecule detection. With the recent experimental advances in water filling of isolated CNTs, the Lucas-Washburn theory for capillary rise in tubes needs to be revisited for a better understanding of the physics and dynamics of water filling in CNTs. Here, the Lucas-Washburn theory is corrected for the hydrodynamic entrance effects as well as the variation of capillary pressure and hydrodynamic properties with the radius and length of CNTs. Due to the large slippage in CNTs, inclusion of the entrance effects is important particularly for the initial stages of filling where a L ∝ t scaling, as opposed to L 2 ∝ t , is observed in our molecular dynamics (MD) simulations. The corrected Lucas-Washburn theory is shown to predict the water filling dynamics in CNTs as observed in MD simulations. With the corrected theory, we achieve a better understanding of capillary rise and water filling dynamics in CNTs.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Effect of interfacial vibrational coupling on surface wettability and water transport

Here, we report that the atomic-scale vibrational coupling at the solid-fluid interface can substantially alter the interfacial properties such as wettability and fluid slip. The wettability of water droplets on substrates subjected to various vibrational frequencies is studied using molecular dynamics simulation. The contact angle increases (i.e., becomes more hydrophobic) when the oscillation frequency of the substrate matches the intermolecular bending frequency of liquid water. We investigate the underlying mechanism by examining the dynamics of water molecules at the interface and find that the temporal contact between the solid and fluid is shorter when the frequencies match, resulting in weak solid-fluid adsorption. We further report that the vibrational match at the interface reduces wall-fluid friction and enhances water transport through the nanopore. Our findings demonstrate the importance of the atomic-scale vibrational coupling at the solid-fluid interface on the physicochemical behavior of nanodevices and biological nanochannels.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Shaping Dynamical Casimir Photons

Temporal modulation of the quantum vacuum through fast motion of a neutral body or fast changes of its optical properties is known to promote virtual into real photons, the so-called dynamical Casimir effect. Empowering modulation protocols with spatial control could enable the shaping of spectral, spatial, spin, and entanglement properties of the emitted photon pairs. Space–time quantum metasurfaces have been proposed as a platform to realize this physics via modulation of their optical properties. Here, we report the mechanical analog of this phenomenon by considering systems in which the lattice structure undergoes modulation in space and in time. We develop a microscopic theory that applies both to moving mirrors with a modulated surface profile and atomic array meta-mirrors with perturbed lattice configuration. Spatiotemporal modulation enables motion-induced generation of co- and cross-polarized photon pairs that feature frequency-linear momentum entanglement as well as vortex photon pairs featuring frequency-angular momentum entanglement. The proposed space–time dynamical Casimir effect can be interpreted as induced dynamical asymmetry in the quantum vacuum.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Investigating the Effect of Water on the Mechanical Properties of Cellulose from Multiscale Molecular Dynamics Simulations

Classical molecular dynamics (MD) simulations provide insight into the structure and physicochemical properties of materials with atomic resolution. However, the length and time scales accessible to atomistic MD are orders of magnitude smaller than many relevant processes such as the response of a bulk material to experimentally accessible strain rates, which presents challenges when comparing models to experimental measurements. Bottom-up coarse-graining provides a means for systematically mapping atomistic information to lower resolution models to increase the length and time scales achievable by simulation. Cellulose is an abundant carbohydrate biopolymer with applications to many fields of research, such as materials science and renewable energy, due to its desirable mechanical properties and viability for conversion into biofuel. The effect of moisture content on the Young's modulus of cellulose is of special interest due to its native environment often being in the hydrated secondary plant cell wall and the grinding energy requirements for biomass feedstock preprocessing. The current work investigates the effects of water solvent on the Young's modulus of cellulose calculated from coarse-grained MD mechanical stress simulations. The coarse-grained model was parametrized from atomistic MD calculations of cellulose-cellulose potentials of mean force using umbrella sampling techniques under vacuum and solvated conditions. The Young's moduli of the coarse-grained cellulose assemblies parametrized from cellulose in vacuum or solvated in water were computed via mechanical stress simulations to highlight the importance of capturing solvent interactions for modeling the mechanical behavior of cellulose.

BASIC BIOLOGICAL SCIENCES,RADIATION PROTECTION AND↗
DOE OSTI2020

Unmixing Symmetries

The low-lying spectra of atomic nuclei display diverse behaviors, for example, rotational bands, which can be described phenomenologically by simple symmetry groups such as spatial SU(3). This leads to the idea of dynamical symmetry, where the Hamiltonian commutes with the Casimir operator(s) of a group, and is block diagonal in subspaces defined by the group’s irreducible representations or irreps. Detailed microscopic calculations, however, show these symmetries are in fact often strongly mixed and the wave function fragmented across many irreps. More commonly, the fragmentation across members of a band are similar, which is called a quasidynamical symmetry. In this Letter I explicitly, albeit numerically, construct unitary transformations from a quasidynamical symmetry to a dynamical symmetry, adapting the similarity renormalization group (SRG) in order to transform away the symmetry-mixing parts of the Hamiltonian. In this work, the standard SRG produces unsatisfactory results, forcing the induced dynamical symmetry to be dominated by high-weight irreps irrespective of the original decomposition. Using spectral distribution theory to rederive and diagnose standard SRG, I introduce a new form of SRG. The new SRG transforms a quasidynamical symmetry to a dynamical symmetry, that is, unmixes the mixed symmetries, with intuitively more appealing results.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Effects of Field Strength and Silver Nanowire Size on Plasmon-Enhanced N 2 Dissociation

Dissociation of the nitrogen molecule via plasmon-enhanced catalysis using noble metal nanoparticles has been investigated both experimentally and computationally in recent years. However, the mechanism of plasmon-enhanced nitrogen dissociation is still not very clear. In this work, we apply theoretical approaches to examine the dissociation of a nitrogen molecule on atomically-thin Ag n nanowires (n = 6, 8, 10, 12) and a Ag 19 + nanorod. Ehrenfest dynamics provides information about the motion of nuclei during the dynamics process and real-time TDDFT calculations show the electronic transitions and population of electrons over the first 10s of fs time scale. The activation and dissociation of nitrogen is typically enhanced when the electric field strength increases. However, the enhancement is not always monotonic with field strength. As the length of the Ag wire increases, nitrogen is typically easier to dissociate and thus requires lower field strengths, even though the plasmon frequency is lower. The Ag 19 + nanorod leads to faster dissociation of N 2 than the atomically-thin nanowires. Altogether, our detailed study yields insights into the mechanisms involved in plasmon-enhanced N 2 dissociation, as well as provides information about factors that can be used to improve adsorbate activation.

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

Topological quantum interference in a pumped Su-Schrieffer-Heeger lattice

Topological quantum interference emerges from the interplay between quantum mechanics and topology. We present evidence for two types of such interference phenomenon that can result from the quantum dynamics of initial topological states. We realize both types of topological quantum interference in a pumped non-Hermitian Su-Schrieffer-Heeger lattice that can be implemented by creation and coherent control of excitonic states of trapped neutral atoms. On quenching the system from the topological to the gapless phases and then back again, we find that interference patterns develop in the gapless phase and also after switching back to the topological phase. These patterns occur both as many-excitation interferences generated in the presence of pumping the atoms at the end sites, and as one- and two-excitation interferences seen in the absence of pumping when starting with edge excitations. Investigation of the excitation dynamics shows that these interference patterns originate from the topological nature of the initial states and are very different from quantum interferences originating from nontopological states of the lattice. Our results also reveal that unlike well-known situations where topological states are protected against local perturbations, in the non-Hermitian SSH systems resulting from driving the excited-state populations, a local dissipation at each lattice site can suppress both the topological interference and the total population of the lattice.

74 ATOMIC AND MOLECULAR PHYSICS↗