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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 883 records · Page 49
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Transition-state correlations for predicting thermochemistry of adsorbates and surface reactions

Estimating thermochemical properties from linear correlations may provide a pathway to circumvent expensive density functional theory (DFT) calculations for quantities such as pre-exponentials and temperature corrections to DFT energies. Here, in this work, we construct thermochemical scaling relations between C 1 –C 6 n-alkanes in the gas phase and adsorbed alkyl chains extending from several transition metal surfaces, and examine changes in the slope and fit between metals and adsorption sites. We subsequently add –OH, –NH 2 , C$=$O, and C$=$C functional groups to the C 1 –C 6 molecules and demonstrate strong linear correlations for thermochemistry across all species. We broaden the correlations to incorporate transition states of C 1 –C 6 n-alkane dehydrogenation reactions, where thermochemistry for computationally prohibitive transition-state calculations can be quickly assessed. Additionally, we rationalize the linearity of thermochemical correlations based on the composition of the homologous series and theoretical assessments. As an application of the correlations, we estimate pre-exponentials for elementary surface reactions of ethane and propane hydrogenolysis on Ru(0001), which is of relevance to plastic hydrogenolysis. Depending on kinetically important steps, entropic contributions may be necessary to include in certain reaction mechanisms; in contrasting examples, entropies are found to be relatively insignificant for ethane hydrogenolysis but pertinent for propane hydrogenolysis.

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

Proton transfer kinetics of transition metal hydride complexes and implications for fuel-forming reactions

Proton transfer reactions involving transition metal hydride complexes are prevalent in a number of catalytic fuel-forming reactions, where the proton transfer kinetics to or from the metal center can have significant impacts on the efficiency, selectivity, and stability associated with the catalytic cycle. Here, this review correlates the often slow proton transfer rate constants of transition metal hydride complexes to their electronic and structural descriptors and provides perspective on how to exploit these parameters to control proton transfer kinetics to and from the metal center. A toolbox of techniques for experimental determination of proton transfer rate constants is discussed, and case studies where proton transfer rate constant determination informs fuel-forming reactions are highlighted. Opportunities for extending proton transfer kinetic measurements to additional systems are presented, and the importance of synergizing the thermodynamics and kinetics of proton transfer involving transition metal hydride complexes is emphasized.

08 HYDROGEN↗
DOE OSTI2023

Inverter Controls for Smooth Transition Operation of Networked Microgrids

Islanding sections of a distribution grid as microgrids and networking these microgrids offer promising opportunities for improving system reliability; however, this approach may need distributed energy resources (DERs) to switch between grid-connected and islanded operation without affecting the system stability. The Thevenin impedance of the power system at the DER point of common coupling changes due to networking actions. It is critical to have smooth transitions between modes to ensure stable system operation and to avoid nuisance tripping. This paper presents the design of a grid-forming (GFM)-capable inverter control scheme to reliably operate in distribution systems with networked microgrids. Control mechanisms for smooth transitions between grid-following (GFL) and GFM inverter modes are presented. First, we test the control mechanism on a simple two-source power system through electromagnetic transient (EMT) simulations using a digital real-time simulator. Then, we add multiple such DERs to the EMT model of a real-world distribution feeder and demonstrate stable operation between mode transitions during the networking of the microgrids.

grid forming controls↗
DOE OSTI2023

Improved temperature dependence of rate coefficients for rotational state-to-state transitions in H 2 O + H 2 O collisions

Aims. We present an improved database of temperature-dependent rate coefficients for rotational state-to-state transitions in H 2 O + H 2 O collisions. The database includes 231 transitions between the lower para-states of H 2 O and 210 transitions between its lower ortho-states (up toj= 7) and can be employed in cometary and planetary applications up to the temperature of 1000 K. Methods. We developed and applied a new general method that allows the generation of rate coefficients for excitation and quenching processes that automatically satisfy the principle of microscopic reversibility and also helps to cover the range of low collision energies by interpolation of cross sections between the process threshold and the computed data points. Results. We find that in the range of intermediate temperatures, 150

Astronomy & Astrophysics↗
DOE OSTI2025

WLCG transition from X.509 to Tokens: Progress and Outlook

Since 2017, the Worldwide LHC Computing Grid (WLCG) has been working towards enabling token-based authentication and authorization throughout its entire middleware stack.Taking guidance from the WLCG Token Transition Timeline, published in 2022, substantial progress has been achieved not only in making middleware compatible with the use of tokens, but also in understanding the limitations of the WLCG Common JWT Profiles, first published in 2019. Significant scalability experience has been gained from Data Challenge 2024, during which millions of files were transferred with tokens used as credentials - a significant percentage of the total transfers completed.Besides describing the state of affairs in the transition to tokens, revisions to the WLCG token profile, and the evolving road maps, this contribution also covers the corresponding transition from VOMS-Admin to INDIGO-IAM services, with continuing improvements in terms of functionality as well as deployment.

Dack, Thomas [Rutherford Appleton Laboratory]↗
DOE OSTI2022

Simulations of x-ray absorption spectra for CO desorbing from Ru(0001) with transition-potential and time-dependent density functional theory approaches

The desorption of a carbon monoxide molecule from a Ru(0001) surface was studied by means of X-ray Absorption Spectra (XAS) computed with Transition Potential (TP-DFT) and Time Dependent (TD-DFT) DFT methods. By unraveling the evolution of the CO electronic structure upon desorption, we observed that at 2.3 Å from the surface, the CO molecule has already predominantly gas-phase character. While C 1s XAS is quite insensitive to changes in the C–O bond length, the O 1s excitation is very sensitive with the π* coming down in energy upon CO bond stretching, which competes with the increase in orbital energy due to the repulsive interaction with the metallic surface. We show in a systematic way that the TP-DFT method can describe the XAS rather well at the endpoints (chemisorbed and gas phase) but is affected by artificial charge transfer and/or incorrect spin treatment in the transition region in cases like CO, where there are low-lying π* orbitals and large exchange interactions between the core 1s and valence-acceptor π* orbitals. As an alternative, we demonstrate by comparing with experimental data that a linear response approach using TD-DFT employing common exchange-correlation functionals and finite-size clusters can yield a good description of the spectral evolution of the 1s → π* transition with correct spin and gas-to-chemisorbed chemical shifts in good agreement with experiment.

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

Percolation and nanosecond fluctuators in V 2 O 3 films within the metal–insulator transition

Vanadium sesquioxide (V 2 O 3 ) exhibits a metal–insulator transition (MIT) at 160 K between a low temperature, monoclinic, antiferromagnetic Mott insulator and a high temperature, rhombohedral, paramagnetic, metallic phase. In thin films, a percolative transition takes place over a finite temperature range of phase coexistence. We study the fluctuating dynamics of this percolative MIT by measuring voltage noise spectra at both low frequencies (up to 100 kHz) and radio frequencies (between 10 MHz and 1 GHz). Noise intensity quadratic in bias is observed in the MIT region, as expected for resistive fluctuations probed nonperturbatively by the current. The low frequency noise resembles flicker-type 1/f β noise, often taking on the form of Lorentzian noise dominated by a small number of fluctuators as the volume fraction of the insulating phase dominates. Radio frequency noise intensity also quadratic in the bias current allows the identification of resistance fluctuations with lifetimes below 1 ns, approaching timescales seen in non-equilibrium pump–probe studies of the transition. We find quantitative consistency with a model for fluctuations in the percolative fraction. The thermodynamics of the MIT suggests that dominant fluctuations are ones that alter small volumes affecting the connectivity of domain boundaries. This noise serves as a sensitive and nonperturbative probe for the dynamics of switching phenomena in this system.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Revealing the nature of electron correlation in transition metal complexes with symmetry breaking and chemical intuition

Here, in this work, we provide a nuanced view of electron correlation in the context of transition metal complexes, reconciling computational characterization via spin and spatial symmetry breaking in single-reference methods with qualitative concepts from ligand-field and molecular orbital theories. These insights provide the tools to reliably diagnose the multi-reference character, and our analysis reveals that while strong (i.e., static) correlation can be found in linear molecules (e.g., diatomics) and weakly bound and antiferromagnetically coupled (monometal-noninnocent ligand or multi-metal) complexes, it is rarely found in the ground-states of mono-transition-metal complexes. This leads to a picture of static correlation that is no more complex for transition metals than it is, e.g., for organic biradicaloids. In contrast, the ability of organometallic species to form more complex interactions, involving both ligand-to-metal σ-donation and metal-to-ligand π-backdonation, places a larger burden on a theory's treatment of dynamic correlation. We hypothesize that chemical bonds in which inter-electron pair correlation is non-negligible cannot be adequately described by theories using MP2 correlation energies and indeed find large errors vs experiment for carbonyl-dissociation energies from double-hybrid density functionals. A theory's description of dynamic correlation (and to a less important extent, delocalization error), which affects relative spin-state energetics and thus spin symmetry breaking, is found to govern the efficacy of its use to diagnose static correlation.

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

Quantifying a partial polyamorphic transition in a cerium-based metallic glass during cooling

Cerium-based metallic glasses are prototype polyamorphous systems with pressure-induced polyamorphic transitions extensively reported. Cooling typically has a similar effect on materials as compression with regard to reducing volume. However, previous studies show dramatically different behavior of Ce-based metallic glasses between cooling and compression, whose origin remains unclear. Here, using in situ low-temperature synchrotron high-energy x-ray diffraction, the structural evolution of a Ce68Al10Cu20Co2 metallic glass is accurately determined and analyzed by a structure factor and a reduced pair distribution function (PDF) during cooling from 298 to 83 K. An unusually large linear thermal expansion coefficient is revealed, which is associated with both continuous but inconsistent structural changes between the two subpeaks of the first atomic shell in terms of average bond lengths and coordination numbers. These phenomena are suggested to be attributed to a gradual 4f electron delocalization of only a minimal amount (∼2.6% at 83 K) of Ce atoms by quantitative analysis of the PDF data. However, a previously expected global polymorphic transition from a low-density amorphous state to a high-density amorphous state with an abrupt volume collapse is not observed. Moreover, electrical resistivity also shows a continuous increase during cooling without any sharp change. It is clarified that cryogenic temperatures could facilitate but are not powerful enough alone to trigger a global polymorphic transition in the Ce68Al10Cu20Co2 metallic glass, suggesting a wide distribution of its local atomic environment.

Chen, Zhi↗
DOE OSTI2021

Causality, intermittence, and crossphase evolution during confinement transitions in the TJ-II stellarator

In this work, we study spontaneous electron to ion root transitions in TJ-II using Langmuir probes. By scanning the probe position on a shot to shot basis, we reconstruct a spatiotemporal map of the evolution of important turbulent quantities in the plasma edge region. We pay particular attention to the evolution of the cross phase between transport-relevant variables, showing the spatiotemporal evolution of this quantity for the first time, revealing the outward propagation of the changes associated with the transition. Additionally, we also compute the intermittence parameter, which allows us to conclude that the turbulence, although its amplitude increases, condenses in a reduced number of dominant modes and becomes less bursty. The causal relationship between variables is studied using the transfer entropy, clarifying the interactions between the main variables and offering a rather complete picture of the complex evolution of the plasma across the confinement transition.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Nature of the bonded-to-atomic transition in liquid silica to TPa pressures

First-principles calculations and analysis of the thermodynamic, structural, and electronic properties of liquid SiO 2 characterize the bonded-to-atomic transition at 0.1–1.6 TPa and 10 4 –10 5 K (1–9 eV), the high-energy-density regime relevant to understanding planetary interiors. We find strong ionic bonds that become short-lived due to high kinetics during the transition, with sensitivity of the transition temperature to pressure, and our calculated Hugoniots agree with past experimental data. Furthermore, these results reconcile previous experimental and theoretical findings by clarifying the nature of the bond dissociation process in early Earth and “rocky” (oxide) constituents of large planets.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Molecular orbital projectors in non-empirical jmDFT recover exact conditions in transition-metal chemistry

Low-cost, non-empirical corrections to semi-local density functional theory are essential for accurately modeling transition-metal chemistry. Here, we demonstrate the judiciously modified density functional theory (jmDFT) approach with non-empirical U and J parameters obtained directly from frontier orbital energetics on a series of transition-metal complexes. We curate a set of nine representative Ti(III) and V(IV) d 1 transition-metal complexes and evaluate their flat-plane errors along the fractional spin and charge lines. We demonstrate that while jmDFT improves upon both DFT+U and semi-local DFT with the standard atomic orbital projectors (AOPs), it does so inefficiently. We rationalize these inefficiencies by quantifying hybridization in the relevant frontier orbitals. To overcome these limitations, we introduce a procedure for computing a molecular orbital projector (MOP) basis for use with jmDFT. We demonstrate this single set of d 1 MOPs to be suitable for nearly eliminating all energetic delocalization and static correlation errors. In all cases, MOP jmDFT outperforms AOP jmDFT, and it eliminates most flat-plane errors at non-empirical values. Unlike DFT+U or hybrid functionals, jmDFT nearly eliminates energetic delocalization and static correlation errors within a non-empirical framework.

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

Transition from ITG to MTM linear instabilities near pedestals of high density plasmas

Here, investigation of linear gyrokinetic ion-scale modes ( k θ ρ s = 0.3) finds that a transition from ion temperature gradient to microtearing mode (MTM) dominance occurs as the density is increased near the pedestal region of a parameterized DIII-D sized tokamak. H-modes profile densities, temperatures, and equilibria are parameterized utilizing the OMFIT PRO_create module. With these profiles, linear gyrokinetic ion-scale instabilities are predicted with CGYRO. This transition (nMTM) has a weak dependence on radial location in the region near the top of the pedestal ( ρ = 0.7 – 0.9), which allows simulating single radii to examine the approximate scaling of nMTM with global parameters. The critical nMTM is found to scale with plasma current. Additionally, increasing the minor radius by decreasing the aspect ratio and increasing the major radius are found to reduce nMTM. However, any relationship between nMTM and density limit physics remains unclear as nMTM increases relative to the Greenwald density with larger minor radius and with larger magnetic field, suggesting that the transport due to MTM may be less important for a reactor. Additionally, nMTM is sensitive to the pedestal temperature, the local electron and ion gradients, the ratio of ion to electron temperature T i / T e, and the current profile. MTMs are predicted to be the dominant instability in the core at similar Greenwald fractions for DIII-D, NSTX, and NSTX-U H-mode experiments, supporting the results of the parameterized study. Additionally, MTMs continue to be the dominant linear instability in a DIII-D L-mode after an H–L transition as the plasma approaches a density limit disruption despite the large change in plasma profiles.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Chapman–Jouguet deflagration criteria and compressibility dynamics of turbulent fast flames for turbulence-induced deflagration-to-detonation transition

This work characterizes the compressibility dynamics in turbulent fast flames for a range of turbulent flame speeds. These turbulent fast flames experience increased effects of compressibility through the formation of strong shocks and may develop a runaway acceleration combined with a pressure buildup that leads to turbulence induced deflagration-to-detonation transition (tDDT). Simultaneous high-speed particle image velocimetry, OH* chemiluminescence, schlieren, and pressure measurements are used to examine the reacting flow field and flame dynamics. We examine flames with turbulent flame speeds ranging from 100 to 600 m/s. At lower turbulent flame speeds, the flame is not able to produce favorable background conditions for deflagration-to-detonation transition (DDT) onset, and thus flame compressibility and turbulence amplification are less dominant, resulting in a weaker acoustic coupling between the flame and compressed region. As the turbulent burning velocities exceed the Chapman–Jouguet deflagration speed, favorable background conditions are produced, as we observe flame-generated shocks and flame-generated turbulence with higher turbulent velocities and larger turbulent scales. At this regime, the flame is categorized to be at the runaway transition regime that leads to tDDT.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Variational deep learning of equilibrium transition path ensembles

Here, we present a time-dependent variational method to learn the mechanisms of equilibrium reactive processes and efficiently evaluate their rates within a transition path ensemble. This approach builds off of the variational path sampling methodology by approximating the time-dependent commitment probability within a neural network ansatz. The reaction mechanisms inferred through this approach are elucidated by a novel decomposition of the rate in terms of the components of a stochastic path action conditioned on a transition. This decomposition affords an ability to resolve the typical contribution of each reactive mode and their couplings to the rare event. The associated rate evaluation is variational and systematically improvable through the development of a cumulant expansion. We demonstrate this method in both over- and under-damped stochastic equations of motion, in low-dimensional model systems, and in the isomerization of a solvated alanine dipeptide. In all examples, we find that we can obtain quantitatively accurate estimates of the rates of the reactive events with minimal trajectory statistics and gain unique insights into transitions through the analysis of their commitment probability.

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

On the nature of two-photon transitions for a collection of molecules in a Fabry–Perot cavity

Here, we investigate the effect of a cavity on nonlinear two-photon transitions of a molecular system and we analyze how such an effect depends on the cavity quality factor, the field enhancement, and the possibility of dephasing. We find that the molecular response to strong light fields in a cavity with a variable quality factor can be understood as arising from a balance between (i) the ability of the cavity to enhance the field of an external probe and promote multiphoton transitions more easily and (ii) the fact that the strict selection rules on multiphoton transitions in a cavity support only one resonant frequency within the excitation range. Although our simulations use a classical level description of the radiation field (i.e., we solve Maxwell–Bloch or Maxwell–Liouville equations within the Ehrenfest approximation for the field–molecule interaction), based on experience with this level of approximation in the past studies of plasmonic and polaritonic systems, we believe that our results are valid over a wide range of external probing.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Hyperfine interactions for small systems including transition-metal elements using self-interaction corrected density-functional theory

The interactions between the electronic magnetic moment and the nuclear spin moment, i.e., magnetic hyperfine (HF) interactions, play an important role in understanding electronic properties of magnetic systems and in realizing platforms for quantum information science applications. We investigate the HF interactions for atomic systems and small molecules, including Ti or Mn, by using Fermi–Löwdin orbital (FLO) based self-interaction corrected (SIC) density-functional theory. We calculate the Fermi contact (FC) and spin-dipole terms for the systems within the local density approximation (LDA) in the FLO-SIC method and compare them with the corresponding values without SIC within the LDA and generalized-gradient approximation (GGA), as well as experimental data. For the moderately heavy atomic systems (atomic number Z ≤ 25), we find that the mean absolute error of the FLO-SIC FC term is about 27 MHz (percentage error is 6.4%), while that of the LDA and GGA results is almost double that. Therefore, in this case, the FLO-SIC results are in better agreement with the experimental data. For the non-transition-metal molecules, the FLO-SIC FC term has the mean absolute error of 68 MHz, which is comparable to both the LDA and GGA results without SIC. For the seven transition-metal-based molecules, the FLO-SIC mean absolute error is 59 MHz, whereas the corresponding LDA and GGA errors are 101 and 82 MHz, respectively. Therefore, for the transition-metal-based molecules, the FLO-SIC FC term agrees better with experiment than the LDA and GGA results. We observe that the FC term from the FLO-SIC calculation is not necessarily larger than that from the LDA or GGA for all the considered systems due to the core spin polarization, in contrast to the expectation that SIC would increase the spin density near atomic nuclei, leading to larger FC terms.

Chemistry↗
DOE OSTI2024

A Jacobian-free pseudo-arclength continuation method for phase transitions in inhomogeneous thermodynamic systems

Developing phase diagrams for inhomogeneous systems in thermodynamics is difficult, in part, due to the large phase space and the possibility of unstable and metastable solutions arising from first-order phase transitions. Pseudo-arclength continuation (PAC) is a method that allows one to trace out stable and unstable solutions of nonlinear systems. Typically, PAC utilizes the Jacobian in order to implement Newton (or quasi-Newton) steps. In this work, we present a Jacobian-free PAC method that is amenable to the usual workflows in inhomogeneous thermodynamics. We demonstrate our method in systems that have first-order phase transitions, including a novel example of polyelectrolyte complex coacervation in confinement, where multiple surface phase transitions occur and can overlap with one another.

Chemistry↗