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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Linear Correlations of Gibbs Free Energy of REE Phosphates (Monazite, Xenotime, and Rhabdophane) and Internally Consistent Binary Mixing Properties

Rare Earth Elements (REE) phosphates (monazite, xenotime, and rhabdophane) are critical REE-bearing minerals typically formed in hydrothermal and magmatic ore deposits. The thermodynamic properties of those REE minerals are crucial to understanding the solubility, speciation, and transport of REE complexes. However, the standard-state Gibbs free energy of formation (∆G°f) values reported for these minerals in the literature vary by up to 25 kJ mol−1. Here, we present linear free energy relationships that allow the evaluation and estimation of the ∆G°f values at 25 °C and 1 bar for the three minerals from the ionic radius (rREE3+) and the non-solvation Gibbs free energy contribution to the REE3+ aqua ion (∆G°n, REE3+): ∆G°f,monazite − 399.71 rREE3+ = 1.0059 ∆G°n,REE3+ − 2522.51; ∆G°f,xenotime − 344.08 rREE3+ = 0.9909 ∆G°n,REE3+ − 2451.53; and ∆G°f,rhabdophane − 416.17 rREE3+ = 1.0067 ∆G°n, REE3+ − 2688.86. Moreover, based on the new dataset derived for REE end-members, we re-fitted the binary Margules parameter (W) from previous theoretical calculations into linear correlations: W + 0.00204 ∆G°’n,monazite = 39.3549 ∆V + 0.0641; W + 0.00255 ∆G°’n,xenotime = 25.4885 ∆V − 0.0062. The internally consistent thermodynamic properties of these REE phosphates are incorporated into the computer program Supcrtbl, which is available online at Zhu’s research website.

Pan, Ruiguang (ORCID:0000000324896545)↗
DOE OSTI2020

Curvature-slope correlation of nuclear symmetry energy and its imprints on the crust-core transition, radius, and tidal deformability of canonical neutron stars

Background: The nuclear symmetry energy E sym (ρ) encodes information about the energy necessary to make nuclear systems more neutron-rich. While its slope parameter L at the saturation density ρ 0 of nuclear matter has been relatively well constrained by recent astrophysical observations and terrestrial nuclear experiments, its curvature K sym characterizing the E sym (ρ) around 2ρ 0 remains largely unconstrained. Over 520 calculations for E sym (ρ) using various nuclear theories and interactions in the literature have predicted several significantly different K sym –L correlations. Purpose: If a unique K sym –L correlation of E sym (ρ) can be firmly established, it will enable us to progressively better constrain the high-density behavior of E sym (ρ) using the available constraints on its slope parameter L. Here, we investigate if and by how much the different K sym –L correlations may affect neutron star observables. Method: A meta-model of nuclear Equation of States (EOSs) with three representative K sym –L correlation functions is used to generate multiple EOSs for neutron stars. We then examine effects of the K sym –L correlation on the crust-core transition density and pressure as well as the radius and tidal deformation of canonical neutron stars. Results: The K sym –L correlation affects significantly both the crust-core transition density and pressure. It also has strong imprints on the radius and tidal deformability of canonical neutron stars especially at small L values. The available data from LIGO/VIRGO and NICER set some useful limits for the slope L but can not distinguish the three representative K sym –L correlations considered.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Stopping-power enhancement from discrete particle-wake correlations in high-energy-density plasmas

Three-dimensional (3D) simulations of electron beams propagating in high-energy-density plasmas using the quasistatic Particle-in-Cell (PIC) code QuickPIC demonstrate a significant increase in stopping power when beam electrons mutually interact via their wakes. Each beam electron excites a plasma wave wake of wavelength ~ 2 π c / ω p e , where c is the speed of light and ω p e is the background plasma frequency. Here we show that a discrete collection of electrons undergoes a beam-plasma-like instability caused by mutual particle-wake interactions that causes electrons to bunch in the beam, even for beam densities n b for which fluid theory breaks down. This bunching enhances the beam's stopping power, which we call “correlated stopping,” and the effect increases with the “correlation number” N b ≡ n b ( c / ω p e ) 3 . For example, a beam of monoenergetic 9.7 MeV electrons with N b = 1 / 8 , in a cold background plasma with n e = 10 26 cm – 3 (450 g cm – 3 DT), has a stopping power of 2.28 ± 0.04 times the single-electron value, which increases to 1220 ± 5 for N b = 64 . The beam also experiences transverse filamentation, which eventually limits the stopping enhancement.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS2018

Li(+)-ligand Binding Energies and the Effect of Ligand Fluorination on the Binding Energies

The Li(+)-ligand binding energies are computed for seven ligands and their perfluoro analogs using Density Functional Theory. The bonding is mostly electrostatic in origin. Thus the size of the binding energy tends to correlate with the ligand dipole moment, however, the charge-induced dipole contribution can be sufficiently large to affect the dipole-binding energy correlation. The perfluoro species are significantly less strongly bound than their parents, because the electron withdrawing power of the fluorine reduces the ligand dipole moment.

Charles W Bauschlicher↗
DOE OSTI2025

The balance of orbital overlap and orbital energy in the activation of methane by actinide cations: insights from inductively coupled plasma tandem mass spectrometry

The actinides present a unique challenge to chemical theory. The classical view of covalent bonding is driven by the extent of spatial overlap of valence orbitals. Modern theory has expanded assessments of covalency to include considerations of orbital energy degeneracy to assess orbital energy mixing between metal and ligand valence orbitals. Actinide–ligand (An–L) bonding has more recently been described as a balance between orbital overlap and orbital energy mixing, where 5f and L valence orbital overlap decreases while energy mixing between An 5f and L valence orbitals increases across the series. To test these existing views, we employed inductively coupled plasma tandem mass spectrometry to examine the kinetic energy dependences of reactions of actinide cations, Th + –Am + , with methane. Further, this is the first experimental report of the energy dependences of methane activation reactions involving the cations of Pa, Np, Pu, and Am and the first experimental determination of transuranic An + –D, An + –CD 2 , An + –CD 3 , and An + –CD bond dissociation energies. The correlation of the measured An + –CD 2 bond energies with E p (6d 2 ) indicates that An + 6d orbitals are the dominant contributors in the An + –CD 2 bonds. Close examination of the relative reactivities of An + offers additional support that the balance of classical and modern views of molecular bonding may lie between Np + and Pu + and that the increased reactivity of Th + –Np + may be attributed to the increased spatial extension of the 5f orbitals whereas covalent An + bond formation may be more driven by the decreasing energies of the 5f orbitals across the actinide series.

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

Time-Resolved Spectroscopy of Insulator-Metal Transitions: Exploring Low-Energy Dynamics in Strongly Correlated Systems. Final Report

Transition metal oxides (TMOs) have attracted much attention in recent years. The strong coupling between charge, spin, and orbital degrees of freedom creates novel functional properties. The research at the interplay between ferromagnetism, ferroelectricity and conductivity provides a promising way to the development of future spintronic devices. The interface characterization of multifunctional oxide heterostructures is crucial to understand deeply the magnetic response, spin injection and spin transport. In year one, we characterized optically the magnetic property with the method of magnetization-induced second-harmonic generation (MSHG), which is a sensitive technique to selectively probe the interface where the spatial inversion symmetry is broken. The interface of n-type BaTiO 3 (BTO)/La 0.67 Sr 0.33 MnO 3 (LSMO) forms a Schottky barrier and displays a good diode effect. By applying an external electric field across the sample, we observe the magnetoelectric (ME) coupling effect to modulate the interface magnetization. The voltage dependent magnetic contrast sharply vanishes at positive voltage (applied to LSMO contact) and reveals a ferromagnetic (FM)-to- antiferromagnetic (AFM) transition occurring at the interface, while the magneto-optic Kerr effect (MOKE) indicates that the bulk property is not affected. The strain mediated mechanism and ferroelectric (FE) polarization induced charge medicated mechanism are both discussed, but they do not play an important role in the observed magnetization transition. A new mechanism is proposed - the injected minority spins through strong Hund's interaction with the local magnetic moments at positive voltage weaken the double-exchange interaction of nearby Mn e g electrons, thereby reducing the ferromagnetic (FM) ordering. The dominant superexchange interaction of localized t 2g electrons finally leads to the AFM configuration. By reducing the electron carrier concentration of BTO, a positive voltage shift of the transition is observed. The oxygen richer sample with lower carrier concentration requires a higher voltage to increase the hole doping level of LSMO to induce the interfacial AFM phase. By inserting a thin (1nm) La 0.5 Ca 0.5 MnO 3 layer between BTO and LSMO, the interface magnetic response from LSMO is enhanced. In year two, a non-multiferroic heterostructure SrTiO 3 (STO)/ La 0.5 Ca 0.5 MnO 3 (LCMO)/La 0.67 Sr 0.33 MnO 3 (LSMO) was studied. In this system, the interface FM-AFM transition is observed at negative voltage. The STO layer may act as a hole-donating layer, which induces the hole transfer to LSMO making it overdoped, while the LCMO interlayer at the 0.5 hole doping level displays complicated CE type AFM phase. Thus the AFM phase is dominant at the interface and electron accumulation is required to induce the FM phase by applying a negative voltage. For oxygen rich sample, the magnetic MSHG loop reappears at high positive voltage (around +2.5 V). At high doping level (x > 0.5), LSMO exhibits A-type AFM order, consisting of AFM superexchange coupling between adjacent layers and intralayer FM double-exchange coupling. The less tensile strain of STO and LSMO due to a smaller lattice mismatch as compared to BTO would result in a weaker interlayer coupling . Thus, interfacial A-type AFM order can occur in STO/LCMO/LSMO heterostructure at high hole doping concentration. The study of ME coupling of multifunctional oxide heterostructures is definitely important to the development and performance of future spintronic devices. The results presented here regarding the interfacial magnetic transition controlled by an external electric field offer some new perspective to study the spin transport of magnetic tunnel junctions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

An in-silico NMR laboratory for nuclear magnetic shieldings computed via finite fields: Exploring nucleus-specific renormalizations of MP2 and MP3

Here we developed and implemented a method-independent, fully numerical, finite difference approach to calculating nuclear magnetic resonance shieldings, using gauge-including atomic orbitals. The resulting capability can be used to explore non-standard methods, given only the energy as a function of finite-applied magnetic fields and nuclear spins. For example, standard second-order Møller-Plesset theory (MP2) has well-known efficacy for 1H and 13C shieldings and known limitations for other nuclei such as 15N and 17O. It is, therefore, interesting to seek methods that offer good accuracy for 15N and 17O shieldings without greatly increased compute costs, as well as exploring whether such methods can further improve 1H and 13C shieldings. Using a small molecule test set of 28 species, we assessed two alternatives: κ regularized MP2 (κ-MP2), which provides energy-dependent damping of large amplitudes, and MP2.X, which includes a variable fraction, X, of third-order correlation (MP3). The aug-cc-pVTZ basis was used, and coupled cluster with singles and doubles and perturbative triples [CCSD(T)] results were taken as reference values. Our κ-MP2 results reveal significant improvements over MP2 for 13C and 15N, with the optimal κ value being element-specific. κ-MP2 with κ = 2 offers a 30% rms error reduction over MP2. For 15N, κ-MP2 with κ = 1.1 provides a 90% error reduction vs MP2 and a 60% error reduction vs CCSD. On the other hand, MP2.X with a scaling factor of 0.6 outperformed CCSD for all heavy nuclei. These results can be understood as providing renormalization of doubles amplitudes to partially account for neglected triple and higher substitutions and offer promising opportunities for future applications.

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

Advances and Challenges of SCAN and r 2 SCAN Density Functionals in Transition‐Metal Compounds

ABSTRACT Transition‐metal compounds (TMCs) with open‐shell d ‐electrons are characterized by a complex interplay of lattice, charge, orbital, and spin degrees of freedom, giving rise to various fascinating applications. Often exhibiting exotic properties, these compounds are commonly classified as correlated systems due to strong inter‐electronic interactions called Hubbard U . This inherent complexity presents significant challenges to Kohn‐Sham density functional theory (KS‐DFT), the most widely used electronic structure method in condensed matter physics and materials science. While KS‐DFT is, in principle, exact for the ground‐state total energy, its exchange‐correlation energy must be approximated in practice. The mean‐field nature of KS implementations, combined with the limitations of current exchange‐correlation density functional approximations, has led to the perception that DFT is inadequate for correlated systems, particularly TMCs. Consequently, a common workaround involves augmenting DFT with an on‐site Hubbard‐like U correction. In recent years, the strongly constrained and appropriately normed (SCAN) density functional, along with its refined variant r 2 SCAN, has achieved remarkable progress in accurately describing the structural, energetic, electronic, magnetic, and vibrational properties of TMCs, challenging the traditional perception of DFT's limitations. This review explores the design principles of SCAN and r 2 SCAN, highlights their key advancements in studying TMCs, explains the mechanisms driving these improvements, and addresses the remaining challenges in this evolving field.

Zhang, Yubo [Minjiang Collaborative Center for The↗
DOE OSTI2021

Fully variational incremental CASSCF

We report the complete-active-space self-consistent field (CASSCF) method is a canonical electronic structure theory that holds a central place in conceptualizing and practicing first principles simulations. For application to realistic molecules, however, the CASSCF must be approximated to circumvent its exponentially scaling computational costs. Applying the many-body expansion - also known as the method of increments - to CASSCF (iCASSCF) has been shown to produce a polynomially scaling method that retains much of the accuracy of the parent theory and is capable of treating full valence active spaces. Due to an approximation made in the orbital gradient, the orbital parameters of the original iCASSCF formulation could not be variationally optimized, which limited the accuracy of its nuclear gradient. Herein, a variational iCASSCF is introduced and implemented, where all parameters are fully optimized during energy minimization. This method is able to recover electronic correlations from the full valence space in large systems, produce accurate gradients, and optimize stable geometries as well as transition states. Demonstrations on challenging test cases, such as the oxoMn(salen)Cl complex with 84 electrons in 84 orbitals and the automerization of cyclobutadiene, show that the fully variational iCASSCF is a powerful tool for describing challenging molecular chemistries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2012

Outburst of GX304-1 Monitored with INTEGRAL: Positive Correlation Between the Cyclotron Line Energy and Flux

Context. X-ray spectra of many accreting pulsars exhibit significant variations as a function of flux and thus of mass accretion rate. In some of these pulsars, the centroid energy of the cyclotron line(s), which characterizes the magnetic field strength at the site of the X-ray emission, has been found to vary systematically with flux. Aims. GX304-1 is a recently established cyclotron line source with a line energy around 50 keV. Since 2009, the pulsar shows regular outbursts with the peak flux exceeding one Crab. We analyze the INTEGRAL observations of the source during its outburst in January-February 2012. Methods. The observations covered almost the entire outburst, allowing us to measure the source's broad-band X-my spectrum at different flux levels. We report on the variations in the spectral parameters with luminosity and focus on the variations in the cyclotron line. Results. The centroid energy of the line is found to be positively correlated with the luminosity. We interpret this result as a manifestation of the local sub-Eddington (sub-critical) accretion regime operating in the source.

Klochkov, D.↗
DOE OSTI2023

Correlated particle transport enables biological free energy transduction

Studies of biological transport frequently neglect the explicit statistical correlations among particle site occupancies (i.e., they use a mean-field approximation). Neglecting correlations sometimes captures biological function, even for out-of-equilibrium and interacting systems. Here, we show that neglecting correlations fails to describe free energy transduction, mistakenly predicting an abundance of slippage and energy dissipation, even for networks that are near reversible and lack interactions among particle sites. Interestingly, linear charge transport chains are well described without including correlations, even for networks that are driven and include site-site interactions typical of biological electron transfer chains. We examine three specific bioenergetic networks: a linear electron transfer chain (as found in bacterial nanowires), a near-reversible electron bifurcation network (as in complex III of respiration and other recently discovered structures), and a redox-coupled proton pump (as in complex IV of respiration).

bacterial nanowires↗
NASA NTRS1978

Correlated electric field and low-energy electron measurements in the low-altitude polar cusp

Correlated electric field and low-energy electron measurements are presented for two passes of Hawkeye 1 through the south polar cusp at 2000-km altitude during local morning. In one case the electric field reversal coincides with the boundary of detectable 5.2keV electron intensities and the equatorward boundary of the cusp. In the other case the electric field reversal and the 5.2 keV electron trapping boundary coincide, but the equatorward edge of the cusp as determined from the presence of 180 eV electron intensities is 5 degrees invariant latitude equatorward of the electric field reversal. It is concluded that in the second case, electron intensities associated with the polar cusp populate closed dayside field lines, and hence the corresponding equatorward edge of these electron intensities is not always an indicator of the boundary between closed dayside field lines and polar cap field lines.

Kintner, P. M.↗
DOE OSTI2024

In-situ digital image correlation and thermal monitoring in directed energy deposition

A method and a system for digital image correlation and thermal monitoring during directed energy deposition are provided. The method and the system include global off-axis 3D mapping of surfaces features at high frame rates using the natural surface roughness of the additive build. Infrared thermography is projected onto these surface features to record the thermo-mechanical history of the finished component. As set forth herein, the method and the system provide a low-cost solution to monitoring and optimizing the unique temporal artifacts induced by complex scan strategies.

Haley, James↗
DOE OSTI2023

Nuclear short-range correlations and the zero-energy eigenstates of the Schrödinger equation

Here, we present a systematic analysis of the nuclear two- and three-body short-range correlations and their relations to the zero-energy eigenstates of the Schrödinger equation. To this end we analyze the doublet and triplet coupled-cluster amplitudes in the high momentum limit, and show that they obey universal equations independent of the number of nucleons and their state. Furthermore, we find that these coupled-cluster amplitudes coincide with the zero-energy Bloch-Horowitz operator. These results illuminate the relations between the nuclear many-body theory and the generalized contact formalism, introduced to describe the nuclear two-body short range correlations, and they might also be helpful for general coupled-cluster computations as the asymptotic part of the amplitudes is given and shown to be universal.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Sparsity of the electron repulsion integral tensor using different localized virtual orbital representations in local second-order Møller–Plesset theory

Utilizing localized orbitals, local correlation theory can reduce the unphysically high system-size scaling of post-Hartree–Fock (post-HF) methods to linear scaling in insulating molecules. The sparsity of the four-index electron repulsion integral (ERI) tensor is central to achieving this reduction. For second-order Møller–Plesset theory (MP2), one of the simplest post-HF methods, only the (ia|jb) ERIs are needed, coupling occupied orbitals i, j and virtuals a, b. In this paper, we compare the numerical sparsity (called the “ragged list”) and two other approaches revealing the low-rank sparsity of the ERI. The ragged list requires only one set of (localized) virtual orbitals, and we find that the orthogonal valence virtual-hard virtual set of virtuals originally proposed by Subotnik et al. gives the sparsest ERI tensor. To further compress the ERI tensor, the pair natural orbital (PNO) type representation uses different sets of virtual orbitals for different occupied orbital pairs, while the occupied-specific virtual (OSV) approach uses different virtuals for each occupied orbital. Here, our results indicate that while the low-rank PNO representation achieves significant rank reduction, it also requires more memory than the ragged list. The OSV approach requires similar memory to that of the ragged list, but it involves greater algorithmic complexity. An approximation (called the “fixed sparsity pattern”) for solving the local MP2 equations using the numerically sparse ERI tensor is proposed and tested to be sufficiently accurate and to have highly controllable error. A low-scaling local MP2 algorithm based on the ragged list and the fixed sparsity pattern is therefore promising.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2012

Search for a Correlation Between Very-High-Energy Gamma Rays and Giant Radio Pulses in the Crab Pulsar

We present the results of a joint observational campaign between the Green Bank radio telescope and the VERITAS gamma-ray telescope, which searched for a correlation between the emission of very-high-energy (VHE) gamma rays ( E(sub Gamma) > 150 GeV) and giant radio pulses (GRPs) from the Crab pulsar at 8.9 GHz. A total of 15,366 GRPs were recorded during 11.6 hr of simultaneous observations, which were made across four nights in 2008 December and in 2009 November and December. We searched for an enhancement of the pulsed gamma-ray emission within time windows placed around the arrival time of the GRP events. In total, eight different time windows with durations ranging from 0.033 ms to 72 s were positioned at three different locations relative to the GRP to search for enhanced gamma-ray emission which lagged, led, or was concurrent with, the GRP event. Furthermore, we performed separate searches on main pulse GRPs and interpulse GRPs and on the most energetic GRPs in our data sample. No significant enhancement of pulsed VHE emission was found in any of the preformed searches. We set upper limits of 5-10 times the average VHE flux of the Crab pulsar on the flux simultaneous with interpulse GRPs on single-rotation-period timescales. On approx. 8 s timescales around interpulse GRPs, we set an upper limit of 2-3 times the average VHE flux. Within the framework of recent models for pulsed VHE emission from the Crab pulsar, the expected VHE-GRP emission correlations are below the derived limits.

RADIO↗