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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Structural Stability of Graphene-Supported Pt Layers: Diffusion Monte Carlo and Density Functional Theory Calculations

In this study, we used a combination of diffusion Monte Carlo and density functional theory calculations to investigate the stability and interlayer binding of various layered structures of Pt atoms adsorbed on graphene. Our findings show that vertically buckled Pt monolayer and bilayer with (111)-packing order are more energetically favorable than the corresponding buckled (100) or flat (100)-packing structures. This can be attributed to the significant lattice mismatch (>10%) between pristine graphene and a free-standing (100)-packing Pt layer. Additionally, our calculations reveal that among the (100)-packing Pt layers, an incommensurate structure with a Pt/C atomic ratio less than 1/2 may be more stable than the commensurate structures registered at the bridge sites, which aligns with recent experimental findings of incommensurate (100)-packing Pt layers on graphene. The interlayer binding between the Pt layer and graphene is found to be primarily driven by van der Waals interaction, except for the AA-stacked buckled-(100) Pt bilayer where the bottom Pt atoms show chemisorption to the graphene surface. In conclusion, this research offers a comprehensive examination of the stability and interlayer binding of metallic Pt layers, providing valuable insights for potential applications as a next-generation catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

An Algorithm for Atom-Centered Lossy Compression of the Atomic Orbital Basis in Density Functional Theory Calculations

Large atomic-orbital (AO) basis sets of at least triple and preferably quadruple-ζ (QZ) size are required to adequately converge Kohn–Sham density functional theory (DFT) calculations toward the complete basis set limit. However, incrementing the cardinal number by one nearly doubles the AO basis dimension, and the computational cost scales as the cube of the AO dimension, so this is very computationally demanding. Here, in this work, we develop and test a threshold-based natural atomic orbital (NAO) scheme in which ϵ-NAOs are obtained as eigenfunctions of atomic blocks of the density matrix in a one-center orthogonalized representation. This enables compression of the AO basis that is optimal for a given threshold, 10 –ϵ , by discarding NAOs with occupation numbers below that threshold. Extensive pilot test calculations using the Hartree–Fock functional and taking the converged density matrix as input suggest that a threshold of 10 –5 can yield a compression factor (ratio of AO to compressed ϵ-NAO dimension) between 2.5 and 4.5 for the QZ pc-3 basis. The errors in relative energies are typically less than 0.1 kcal/mol when the compressed basis is used instead of the uncompressed basis. Between 10 and 100 times smaller errors (i.e., usually less than 0.01 kcal/mol) can be obtained with a threshold 10 –7 , while the compression factor is typically between 2 and 2.5.

basis sets↗
NASA NTRS2002

Electronic Absorption Spectra of Neutral Perylene (C20H12), Terrylene (C30H16), and Quaterrylene (C40H20) and their Positive and Negative Ions: Ne Matrix-Isolation Spectroscopy and Time Dependent Density Functional Theory Calculations

We present a full experimental and theoretical study of an interesting series of polycyclic aromatic hydrocarbons, the oligorylenes. The absorption spectra of perylene, terrylene and quaterrylene in neutral, cationic and anionic charge states are obtained by matrix-isolation spectroscopy in Ne. The experimental spectra are dominated by a bright state that red shifts with growing molecular size. Excitation energies and state symmetry assignments are supported by calculations using time dependent density functional theory methods. These calculations also provide new insight into the observed trends in oscillator strength and excitation energy for the bright states: the oscillator strength per unit mass of carbon increases along the series.

Halasinski, Thomas M.↗
DOE OSTI2023

Polaron-induced metal-to-insulator transition in vanadium oxides from density functional theory calculations

Vanadium oxides have been extensively studied as phase-change memory units in artificial synapses for neuromorphic computing due to their metal-insulator transitions (MIT) at or near room temperature. Recently, injection of charge carriers into vanadium oxides, e.g., via optically via a heterostructure, has been proposed as an alternative switching mechanism and also potentially as a means to tune the MIT temperature. In this study, we explore the formation of small polarons in the low temperature (LT) insulating phases for V 3 O 5 ,VO 2 , and V 2 O 3 , and the barriers to their migration using density functional theory calculations. We find that V 3 O 5 exhibits very low hole and electron polaron migration barriers (<100 meV) compared to V 2 O 3 and VO 2 , leading to much higher estimated polaronic conductivity. We also link the relative migration barriers to the amount of distortion that has to travel when the polaron migrate from one site to another. Polarons in V 3 O 5 also have smaller binding energies to vanadium and oxygen vacancy defects. Furthermore, these results suggest that the triggering of the MIT via injection of charge carriers are due to the formation of small polarons that can migrate rapidly through the crystal.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

Effects of substitutional Ga on the phonons of δ -phase Pu based on density functional theory calculations

The delta phase of Pu is stabilized by Ga doping, but the mechanism of this stabilization remains an open question. Density functional theory calculations focused on how Ga doping affects the phonons sheds some light on the phonons' contribution to the stabilization. Here, the calculated phonon modes of Ga-doped delta phase Pu fall into two distinct types: localized, high frequency Ga-dominated phonon modes, and Pu-dominated modes at lower frequencies. Increasing the Ga concentration has an effect on the Pu-dominated phonon modes opposite to that of compression: higher-frequency modes soften, and lower-frequency modes stiffen. The latter provides an indication that the stabilization mechanism is not due to a thermodynamic contribution from the phonons. Furthermore, the stiffened phonon modes include candidate modes that describe possible pathways into low-temperature phases, suggesting that doping with Ga could impede such pathways.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Spectral scheme for atomic structure calculations in density functional theory

In this study, we present a spectral scheme for atomic structure calculations in pseudopotential Kohn-Sham density functional theory. In particular, after applying an exponential transformation of the radial coordinates, we employ global polynomial interpolation on a Chebyshev grid, with derivative operators approximated using the Chebyshev differentiation matrix, and integrations using Clenshaw-Curtis quadrature. We demonstrate the accuracy and efficiency of the scheme through spin-polarized and unpolarized calculations for representative atoms, while considering local, semilocal, and hybrid exchange-correlation functionals. In particular, we find that $\mathcal{O}$(200) grid points are sufficient to achieve an accuracy of 1 microhartree in the eigenvalues for optimized norm conserving Vanderbilt pseudopotentials spanning the periodic table from atomic number Ζ = 1 to 83.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Finding the Pareto front for high-entropy-alloy catalysts

Finding catalysts that have both high activity and high stability presents a long-standing challenge. Since optimizing activity and stability are conflicting objectives, the best one can do is find the Pareto front that yields optimal tradeoffs between these features. On the Pareto front, there is a trade-off where a portion of catalytic activity must be sacrificed to gain further stability and vice versa . Here, we provide a method to optimize the front by designing a multi-objective genetic algorithm that combines machine learning, graph neural network calculations, and density functional calculations. The application considered is the oxygen evolution reaction catalyzed by high-entropy alloys. We find that the Pareto front generally contains alloys with diverse elements, but that enhancing stability inevitably inflicts a toll on activity. We compare the general conclusions of our work to a survey of 545 experiments.

Zhang, Chengyi [Univ. of Auckland (New Zealand)]↗
DOE OSTI2021

Optical response and band structure of LiCoO 2 including electron-hole interaction effects

The optical response functions and band structures of LiCoO 2 are studied at different levels of approximation, from density functional theory (DFT) in the generalized gradient approximation (GGA) to quasiparticle self-consistent QSGW (with G for Green's function and W for screened Coulomb interaction) without and with ladder diagrams ($QSG\hat{W}$) and the Bethe Salpeter Equation (BSE) approach. The QSGW method is found to strongly overestimate the band gap and electron-hole or excitonic effects are found to be important. They lower the quasiparticle gap by only about 11~\% but the lowest energy peaks in absorption are found to be excitonic in nature. The contributions from different band to band transitions and the relation of excitons to band-to-band transitions are analyzed. Finally, the excitons are found to be strongly localized. Finally, a comparison to experimental data is presented.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Electronically induced defect creation at semiconductor/oxide interface revealed by time-dependent density functional theory

Carrier induced defect creation at the semiconductor-oxide interface has been known as the origin of electronic device degradation for a long time, but how exactly the interface lattice can be damaged by carriers (especially low-energy ones) remains unclear. Here we carry out real-time time-dependent density functional theory simulations on concrete Si/SiO 2 interfaces to study the interaction between excited electrons and interface bonds. We show that the normal interface Si-H bonds are generally resistant to electrons due to the delocalized nature and high energy level of the Si-H antibonding states, and due to the high-energy barrier to break the Si-H bond. However, if an additional hydrogen atom exists by attaching to a nearby oxygen atom (forming a “Si-H···H-O” complex), the Si-H bond will be greatly weakened, including the reduction of energy barrier for bond breaking, and the lowering of the antibonding state energy level which favors electron injection. Together with the multiple vibrational excitation process, the corresponding Si-H bond can be broken much more easily. Thus we propose that the Si-H···H-O complex will be the center for defect creation and device degradation. Finally, we also explain why such a center might be relatively easy to form during the hydrogen annealing process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Highly accurate and constrained density functional obtained with differentiable programming

Using an end-to-end differentiable implementation of the Kohn-Sham self-consistent field equations, we obtain a highly accurate neural network–based exchange and correlation (XC) functional of the electronic density. The functional is optimized using information on both energy and density while exact constraints are enforced through an appropriate neural network architecture. Here we evaluate our model against different families of XC approximations and show that at the meta-GGA level our functional exhibits unprecedented accuracy for both energy and density predictions. For nonempirical functionals, there is a strong linear correlation between energy and density errors. We use this correlation to define an XC functional quality metric that includes both energy and density errors, leading to an improved way to rank different approximations.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Pure quantum extension of the semiclassical Boltzmann-Uehling-Uhlenbeck equation

The Boltzmann equation is the traditional framework in which one extends the time-dependent mean field classical description of a many-body system to include the effect of particle-particle collisions in an approximate manner. A semiclassical extension of this approach to quantum many-body systems was suggested by Uehling and Uhlenbeck in 1933 for both Fermi and Bose statistics, and many further developments of this approach are known as the Boltzmann-Uehling-Uhlenbeck (BUU) equations. In this paper I introduce a pure quantum version of the BUU type of equations, which is mathematically equivalent to a generalized time-dependent density functional theory extended to superfluid systems. As expected, during nonequilibrium processes the quantum Boltzmann one-body entropy increases during evolution.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS2002

Time Dependent Density Functional Theory Calculations of Large Compact PAH Cations: Implications for the Diffuse Interstellar Bands

We investigate the electronic absorption spectra of several maximally pericondensed polycyclic aromatic hydrocarbon radical cations with time dependent density functional theory calculations. We find interesting trends in the vertical excitation energies and oscillator strengths for this series containing pyrene through circumcoronene, the largest species containing more than 50 carbon atoms. We discuss the implications of these new results for the size and structure distribution of the diffuse interstellar band carriers.

Weisman, Jennifer L.↗
DOE OSTI2024

Reproducibility of real-time time-dependent density functional theory calculations of electronic stopping power in warm dense matter

Real-time time-dependent density functional theory (TDDFT) is widely considered to be the most accurate available method for calculating electronic stopping powers from first principles, but there have been relatively few assessments of the consistency of its predictions across different implementations. This problem is particularly acute in the warm dense regime, where computational costs are high and experimental validation is rare and resource intensive. We report a comprehensive cross-verification of stopping power calculations in conditions relevant to inertial confinement fusion conducted using four different TDDFT implementations. We find excellent agreement among both the post-processed stopping powers and relevant time-resolved quantities for alpha particles in warm dense hydrogen. We also analyze sensitivities to a wide range of methodological details, including the exchange-correlation model, pseudopotentials, initial conditions, observable from which the stopping power is extracted, averaging procedures, projectile trajectory, and finite-size effects. We show that among these details, pseudopotentials, trajectory-dependence, and finite-size effects have the strongest influence, and we discuss different strategies for controlling the latter two considerations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Density functional theory calculations of the mixing enthalpy of ternary uranium carbide compounds

The high melting point of uranium-zirconium carbides (U,Zr)C makes them an ideal fuel for nuclear thermal propulsion (NTP) reactors. Gaps remain in the current understanding of the U-Zr-C system due to the difficulty of conducting thermodynamic experiments at NTP operation conditions. Density functional theory calculations using the Hubbard U model (DFT+U) were performed using orbital matrix occupation (OMC) to obtain the mixing enthalpy for UC and ZrC for (U,Zr)C ternary compounds. Similarly, DFT+U calculations were also carried out for the (U,Nb)C and (U,Ta)C systems. In conclusion, the DFT results are envisioned to be used in thermodynamic assessments of the uranium carbide systems based on the CALPHAD approach to supplement the lack of experimental data for the mixing thermodynamics.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Atomic-Level Structure of Mesoporous Hexagonal Boron Nitride Determined by High-Resolution Solid-State Multinuclear Magnetic Resonance Spectroscopy and Density Functional Theory Calculations

Mesoporous hexagonal boron nitride (p-BN) has received significant attention over the last decade as a promising candidate for water cleaning/pollutant removal and hydrogen storage applications. In this work, high-resolution solid-state NMR spectroscopy and plane-wave density-functional theory (DFT) calculations are used to obtain an atomic-level description of p-BN. 1 H– 15 N or 1 H– 14 N heteronuclear (HETCOR) correlation experiments recorded with either conventional NMR at room temperature or dynamic nuclear polarization surface-enhanced spectroscopy (DNP-SENS) at ca. 100 K reveal NB 2 H, NBH 2 , NBH 3 + species residing on the edges of BN sheets. Ultra-high field 35.2 T 11 B NMR spectroscopy was used to resolve 11 B NMR signals from BN 3 , BN 2 O x (OH) 1–x (x = 0–1), BNO x (OH) 2–x (x = 0–2), BO x (OH) 3–x (x = 0–3), and BO x (OH) 4–x – (x = 0–4). Importantly, 2D 11 B dipolar double-quantum–single-quantum homonuclear correlation spectra reveal that many pore/defect sites are composed of boron oxide/hydroxide clusters connected to the BN framework through BN 2 O units. 1D and 2D 11 B{ 15 N} HETCOR NMR experiments, in addition to plane-wave DFT calculations of nine different structural models, further confirm the assignment of all NMR signals. The detailed structure determination of the pore and edge/defect sites within p-BN should further enable the rational design and development of next-generation p-BN-based materials. In addition, the techniques outlined here should be applicable to determine structure within other porous and/or boron-based materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

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

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

Moldabekov, Zhandos A. [Helmholtz-Zentrum Dresden-↗
DOE OSTI2023

Time-dependent density-functional-theory calculations of the nonlocal electron stopping range for inertial confinement fusion applications

Nonlocal electron transport is important for understanding laser-target coupling for laser-direct-drive (LDD) inertial confinement fusion (ICF) simulations. Current models for the nonlocal electron mean free path in radiation-hydrodynamic codes are based on plasma-physics models developed decades ago; improvements are needed to accurately predict the electron conduction in LDD simulations of ICF target implosions. Here we utilized time-dependent density functional theory (TD-DFT) to calculate the electron stopping power (SP) in the so-called conduction-zone plasmas of polystyrene in a wide range of densities and temperatures relevant to LDD. Compared with the modified Lee-More model, the TD-DFT calculations indicated a lower SP and a higher stopping range for nonlocal electrons. We fit these electron SP calculations to obtain a global analytical model for the electron stopping range as a function of plasma conditions and the nonlocal electron kinetic energy. This model was implemented in the one-dimensional radiation-hydrodynamic code LILAC to perform simulations of LDD ICF implosions, which are further compared with simulations by the standard modified Lee-More model. In conclusion, results from these integrated simulations are discussed in terms of the implications of this TD-DFT-based mean-free-path model to ICF simulations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗