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At least 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Orbital ordering in the layered perovskite material CsVF 4

In strongly correlated electronic systems, several novel physical properties are induced by the orbital degree of freedom. In particular, orbital degeneracy near the Fermi level leads to spontaneous symmetry breaking, such as the nematic state in FeSe and the orbital ordering in several perovskite systems. Here, the novel layered perovskite material CsVF 4 , with a 3 d 2 electronic configuration, was systematically studied using density-functional theory and a multiorbital Hubbard model within the Hatree-Fock approximation. Furthermore, our results show that CsVF 4 should be magnetic, with a G-type antiferromagnetic arrangement in the a b plane and weak antiferromagnetic exchange along the c axis, in agreement with experimental results. Driven by the Jahn-Teller distortion in the VF 6 octahedra that shorten the c axis, the system displays an interesting electron occupancy d x y 1 ( d x z d y z ) 1 corresponding to the lower nondegenerate d x y orbital being half-filled and the other two degenerate d y z and d x z orbitals sharing one electron per site. We show that this degeneracy is broken and a novel d y z / d x z staggered orbital pattern is here predicted by both the first-principles and Hubbard model calculations. This orbital ordering is driven by the electronic instability associated with degeneracy removal to lower the energy.

36 MATERIALS SCIENCE↗
NASA NTRS1973

Solar albedo and spectral reflectance for Apollo 15 and 16 lunar fines

The spectral directional reflectance of Apollo 15 and 16 fines was obtained for bulk densities of approximately 1000 and 1600 kg/cu m. The solar albedo as a function of illumination was calculated from these results. Comparison of solar albedos shows that Apollo 11, 12, and 15 soils fall into one group and the Apollo 14 and 16 soil results into a second group corresponding to mare or lunar highland materials.

Birkebak, R. C.↗
NASA NTRS1997

Auger Spectroscopy of Hydrogenated Diamond Surfaces

An energy shift and a change of the line shape of the carbon core-valence-valence Auger spectra are observed for diamond surfaces after their exposure to an electron beam, or annealing at temperatures higher then 950 C. The effect is studied for both natural diamond crystals and chemical-vapor-deposited diamond films. A theoretical model is proposed for Auger spectra of hydrogenated diamond surfaces. The observed changes of the carbon Auger line shape are shown to be related to the redistribution of the valence-band local density of states caused by the hydrogen desorption from the surface. One-electron calculation of Auger spectra of diamond surfaces with various hydrogen coverages are presented. They are based on self-consistent wave functions and matrix elements calculated in the framework of the local-density approximation and the self-consistent linear muffin-tin orbital method with static core-hole effects taken into account. The major features of experimental spectra are explained.

Krainsky, I. L.↗
NASA NTRS1994

AutoClass: A Bayesian Approach to Classification

We describe a Bayesian approach to the untutored discovery of classes in a set of cases, sometimes called finite mixture separation or clustering. The main difference between clustering and our approach is that we search for the "best" set of class descriptions rather than grouping the cases themselves. We describe our classes in terms of a probability distribution or density function, and the locally maximal posterior probability valued function parameters. We rate our classifications with an approximate joint probability of the data and functional form, marginalizing over the parameters. Approximation is necessitated by the computational complexity of the joint probability. Thus, we marginalize w.r.t. local maxima in the parameter space. We discuss the rationale behind our approach to classification. We give the mathematical development for the basic mixture model and describe the approximations needed for computational tractability. We instantiate the basic model with the discrete Dirichlet distribution and multivariant Gaussian density likelihoods. Then we show some results for both constructed and actual data.

Stutz, John↗
DOE OSTI2025

Time-Dependent Density Functional Theory Description of 238 U⁡(n,f), 240,242 Pu⁢(n,f), and 237 Np(n,f) Reactions

In nuclei with an odd nucleon number the nonvanishing spin number density is the source of a pseudomagnetic field, which favors the splitting of the nucleon Cooper pairs. Such a pseudomagnetic field is generated always in the dynamics of any nucleus, but its effects on Cooper pairs are significantly enhanced in the dynamic evolution of nuclei with an odd number of nucleons. We present for the first time a microscopic study of the induced fission of the odd neutron compound nuclei 239 U, 241,243 Pu, and the odd proton, odd neutron compound nucleus 238 Np, performed within the time-dependent density functional theory extended to superfluid fermion systems, without any simplifying assumptions, with controlled numerical approximations, and for a very large number of initial conditions. Because of the presence of the unpaired odd nucleon(s), the time-reversal symmetry of the fission compound nucleus is spontaneously broken, an aspect routinely neglected in the most advanced microscopic approaches of the past. The emerging fission fragment properties are quite similar to the properties of fission fragments of neighboring even-even nuclei. The time from saddle-to-scission is often significantly longer in odd-odd or odd-mass nuclei than for even-even nuclei, since systems with unpaired nucleons are easier to excite and the potential energy surfaces of these nuclei have more structure, often resembling a very complicated obstacle course, rather than a more direct evolution of the nuclear shape from the top of the outer fission barrier to the scission configuration. The Pauli blocking approximation, often invoked in the literature, expected to inhibit the fission of nuclei with unpaired nucleons, is surprisingly strongly violated during the fission dynamics.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Meta-GGA exchange-correlation free energy density functional to increase the accuracy of warm dense matter simulations

We discuss strategies for thermalization of the ground-state meta-generalized gradient approximation (meta-GGA) exchange-correlation (XC) functionals. A simple but accurate scheme is implemented via universal additive thermal correction to XC using a perturbative-like self-consistent approach. The additive correction with explicit temperature dependence is applied to the ground-state deorbitalized, strongly constrained and appropriately normed (SCAN-L) meta-GGA XC leading to thermal XC functional denoted here as T-SCAN-L. Thermal T-SCAN-L meta-GGA functional shows significant improvement in density functional theory calculation accuracy for warm dense matter by a factor of 3 to 10, achieving unprecedented accuracy of total pressure between a few tenths and 1% when compared to traditional XC functionals, as demonstrated by the comparison to pathintegral Monte Carlo simulations for helium equation of state. Furthermore, the T-SCAN-L calculations of dc conductivity of warm dense aluminum also give better agreement with experiments over other XC functionals such as PBE and SCAN-L.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Electronic correlation induced expansion of Fermi pockets in δ-plutonium

Plutonium is a critically important material as the behavior of its 5f electrons stands midway between the metalliclike itinerant character of the light actinides and localized atomic-core-like character of the heavy actinides. The δ phase of plutonium (δ-Pu), whereas still itinerant, has a large coherent Kondo peak and strong electronic correlations coming from its near-localized character. Here, using sophisticated Gutzwiller wave function and dynamical mean-field theory correlated theories, we study the Fermi surface and associated mass renormalizations of δ-Pu together with calculations of the de Haas–van Alphen frequencies. We find a large (~200%) correlation induced volume expansion in both the hole and the electron pockets of the Fermi surface in addition to an intermediate mass enhancement. All of the correlated electron theories predict, approximately, the same hole pocket placement in the Brillouin zone, which is different from that obtained in conventional density-functional band-structure theory, whereas the electron pockets from all theories are in, roughly, the same place.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Spin waves in doped graphene: A time-dependent spin density functional approach to collective excitations in paramagnetic two-dimensional Dirac fermion gases

In spin-polarized itinerant electron systems, collective spin-wave modes arise from dynamical exchange and correlation (xc) effects. We consider here spin waves in doped paramagnetic graphene with adjustable Zeeman-type band splitting. The spin waves are described using time-dependent spin density functional response theory, treating dynamical xc effects within the Slater and Singwi-Tosi-Land-Sjölander approximations. We obtain spin-wave dispersions and spin stiffnesses as a function of doping and spin polarization, and we discuss the prospects for their experimental observation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

An efficient protocol for excited states of large biochromophores

Efficient energy transport in photosynthetic antenna is a long-standing source of inspiration for artificial light harvesting materials. However, characterizing the excited states of the constituent chromophores poses a considerable challenge to mainstream quantum chemical and semiempirical excited state methods due to their size and complexity and the accuracy required to describe small but functionally important changes in their properties. In this paper, we explore an alternative approach to calculating the excited states of large biochromophores, exemplified by a specific method for calculating the Q y transition of bacteriochlorophyll a, which we name Chl-xTB. Using a diagonally dominant approximation to the Casida equation and a bespoke parameterization scheme, Chl-xTB can match time-dependent density functional theory’s accuracy and semiempirical speed for calculating the potential energy surfaces and absorption spectra of chlorophylls. We demonstrate that Chl-xTB (and other prospective realizations of our protocol) can be integrated into multiscale models, including concurrent excitonic and point-charge embedding frameworks, enabling the analysis of biochromophore networks in a native environment. We exploit this capability to probe the low-frequency spectral densities of excitonic energies and interchromophore interactions in the light harvesting antenna protein LH2 (light harvesting complex 2). The impact of low-frequency protein motion on interchromophore coupling and exciton transport has routinely been ignored due to the prohibitive costs of including it in simulations. Our results provide a more rigorous basis for continued use of this approximation by demonstrating that exciton transition energies are unaffected by low-frequency vibrational coupling to exciton interaction energies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

Quantiles, parametric-select density estimation, and bi-information parameter estimators

A quantile-based approach to statistical analysis and probability modeling of data is presented which formulates statistical inference problems as functional inference problems in which the parameters to be estimated are density functions. Density estimators can be non-parametric (computed independently of model identified) or parametric-select (approximated by finite parametric models that can provide standard models whose fit can be tested). Exponential models and autoregressive models are approximating densities which can be justified as maximum entropy for respectively the entropy of a probability density and the entropy of a quantile density. Applications of these ideas are outlined to the problems of modeling: (1) univariate data; (2) bivariate data and tests for independence; and (3) two samples and likelihood ratios. It is proposed that bi-information estimation of a density function can be developed by analogy to the problem of identification of regression models.

Parzen, E.↗
NASA NTRS1998

Determination of Particle Sources for a Geotail Distribution Function Observed on May 23, 1995

On May 23, 1995, the Comprehensive Plasma Instrumentation (CPI) onboard the Geotail spacecraft observed a complex and structured ion distribution function near the magnetotail midplane at x approximately -10 R(sub E). On the same day, the Wind spacecraft observed a very high density (approximately 40/cubic cm) solar wind and an interplanetary magnetic field (IMF) that was predominantly northward but had several southward turnings. We have inferred the sources of the ions in this distribution function by following approximately 90,000 ion trajectories backward in time using time-dependent electric and magnetic fields obtained from a global MHD (magnetohydrodynamic) simulation. Wind data were used as input for the MHD model. We found that three sources contributed to this distribution: the ionosphere, the plasma mantle which had near-Earth and distant tail components, and the low latitude boundary layer (LLBL). Moreover, distinct structures in the low energy part of the distribution function were found to be associated with individual sources. Structures near 0 deg pitch angle were made up of either ionospheric or plasma mantle ions, while structures near 90 deg pitch angle were dominated by ions from the LLBL source. Particles that underwent nonadiabatic acceleration were numerous in the higher energy part of the ion distribution function, whereas ionospheric and LLBL ions were mostly adiabatic. A large proportion of the near-Earth mantle ions underwent adiabatic acceleration, while most of the distant mantle ions experienced nonadiabatic acceleration.

Ashour-Abdalla, M.↗
DOE OSTI2026

Using Density-Corrected DFT to Understand Density-Driven and Functional-Dependent Errors in Ab Initio Simulations of the Hydrated Electron

The hydrated electron, an excess electron in liquid water, plays a crucial role in a plethora of chemical processes, motivating extensive research efforts to characterize its structure, dynamics, and reactivity in solution. Recent theoretical approaches to understanding this intriguing object have involved ab initio simulations based on density functional theory (DFT). Although DFT allows for the study of hydrated electron reactivity and quantum mechanical behavior, it is well-known that anionic systems can suffer from significant density-driven errors (DDEs). Density-corrected DFT (DC-DFT) provides a framework to mitigate such errors; the method reduces DDEs by replacing the self-consistent (SC) density associated with a given density functional with the Hartree–Fock (HF) density. Since HF densities tend to be more localized than DFT SC densities, the DC-DFT scheme significantly improves errors in calculations where the SC density is spuriously delocalized. Here, we investigate how the use of density correction affects the calculated properties of the DFT-simulated (PBEh) hydrated electron, a particularly challenging diffuse anionic system to simulate. First, we analyze charge delocalization in a system consisting of a model octahedral hydrated electron water cluster (the so-called Kevan structure) along with a spatially separated sulfur atom. We show that the use of density correction indeed reduces DDEs in comparison to a standard DFT global hybrid functional. We then propagate molecular dynamics trajectories of the hydrated electron using DC-DFT, where we find that DC further localizes electron density in the cavity region, a signature of reduced charge delocalization. Unfortunately, the decreased radius of gyration of the spin density and corresponding tightening of the local solvation structure from density correction causes predicted observables to deviate further from experimental measurements than when density correction is not employed. Here, we argue that DC’s worse agreement with experiment results from the removal of a fortuitous cancellation of errors that is intrinsic to the PBEh functional. This indicates that the difficulties with DFT to simulate hydrated electrons are primarily due to the inherent approximations in DFT rather than to density-driven errors.

Density functional theory↗
DOE OSTI2022

A flexible and scalable scheme for mixing computed formation energies from different levels of theory

Abstract Computational materials discovery efforts are enabled by large databases of properties derived from high-throughput density functional theory (DFT), which now contain millions of calculations at the generalized gradient approximation (GGA) level of theory. It is now feasible to carry out high-throughput calculations using more accurate methods, such as meta-GGA DFT; however recomputing an entire database with a higher-fidelity method would not effectively leverage the enormous investment of computational resources embodied in existing (GGA) calculations. Instead, we propose here a general procedure by which higher-fidelity, low-coverage calculations (e.g., meta-GGA calculations for selected chemical systems) can be combined with lower-fidelity, high-coverage calculations (e.g., an existing database of GGA calculations) in a robust and scalable manner. We then use legacy PBE(+ U ) GGA calculations and new r 2 SCAN meta-GGA calculations from the Materials Project database to demonstrate that our scheme improves solid and aqueous phase stability predictions, and discuss practical considerations for its implementation.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Electronic properties and optical spectra of donor–acceptor conjugated organic polymers

Organic semiconductors based on conjugated donor-acceptor (D–A) polymers are a unique platform for electronic, spintronic, and energy-harvesting devices. Understanding the electronic structure of D–A polymers with a small band gap is essential for developing next-generation technologies. Here, we investigate the electronic structure and optical spectra of cyclopentadithiophene-based closed/open-shell D–A polymers using density functional theory and the Bethe–Salpeter equation based on G 0 W 0 approximation. We explored the role of different acceptor units and chemical substitutions on the structural changes and, more importantly, electronic, optical, and dielectric behavior. We found that the computed first exciton peak of the polymers agreed well with the available experimentally measured optical gap. Furthermore, D–A polymers with open-shell character display higher dielectric constant than the closed-shell polymers. We show that the exceptional performance of polycyclopentadithiophene-thiophenylthiadiazoloquinoxaline (PCPDT-TTQ) as a scalable n-type material for Faradaic supercapacitors can be partly ascribed to its elevated dielectric constant. Consequently, these D–A polymers, characterized by their high dielectric constants, exhibit significant potential for various applications, including energy storage, organic electronics, and the production of dielectric films.

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

Probing configurational disorder in ZnGeN 2 using cluster-based Monte Carlo

ZnGeN 2 is sought as a semiconductor with comparable lattice constant to GaN and tunable band gap for integration in optoelectronic devices. Configurational disorder on the cation sublattice of ZnGeN 2 can strongly modify the electronic structure compared to the ordered material, and both ordered and disordered forms of ZnGeN 2 are candidates for light-emitting diodes and other emitters. The nonisovalent character of the disordered species (Zn 2+ and Ge 4+ ) subjects the cation ordering to strong short-range order effects. To model these effects, we use Monte Carlo (MC) simulations utilizing a cluster expansion to approximate formation enthalpy. Representative disordered configurations in 1024-atom supercells are relaxed in density functional theory calculations. From the MC structures, we extract a short-range order parameter (the N-cation coordination motif), and two long-range order parameters (Bragg-Williams and stretching parameters), and examine their correlations. We perform a thermodynamic integration to determine the mixing entropy and free energy. ZnGeN 2 exhibits a first-order phase transition with pronounced discontinuities in enthalpy and entropy, as well as in the structural order parameters. We discuss the relationship between the effective temperature used in the MC simulation and the growth temperatures in experiment in relation to the crossover from the nonequilibrium to the equilibrium growth regime. This work expands on current models of site disorder in ZnGeN 2 and provides atomic structure models with a systematic variation of the degree of cation disorder.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1974

Thermal characteristics of Apollo 16 lunar fines

The vacuum thermal conductivity of the Apollo 16 fines is presented as a function of temperature for the approximate range of diurnal temperatures on the moon. The density used is 1500 kg/cu m, which is approximately the density of the core tube samples returned from the landing site. The thermal diffusivity was calculated from the conductivity, density and specific heat and is also presented. These properties along with the reflectance and emittance are used in a calculation of temperature in the lunar surface layer.

Cremers, C. J.↗
NASA NTRS1974

Thermal conductivity of Apollo 16 lunar fines

The vacuum thermal conductivity of the Apollo 16 fines is presented as a function of temperature for the approximate range of diurnal temperatures on the moon. The density used is 1500 kg/cu m, which is approximately the density of the core-tube samples returned from the landing site. The thermal diffusivity was calculated from the conductivity, density, and specific heat and is also presented.

Cremers, C. J.↗
NASA NTRS1978

Critical currents in sputtered PbMo6S8

Critical currents in sputtered Chevrel-phase lead molybdenum sulfide have been measured at several temperatures as a function of applied magnetic field up to 19 T. A critical current density of approximately 50 million A/sq m was obtained at 15 T and 1.8 K, and the effective upper critical field was estimated to be 30 T. The pinning force at low fields was found to be dependent on the amount of free lead.

Alterovitz, S. A.↗