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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 757 records · Page 42
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Structures and magnetic properties of Ni n (n = 36-40) clusters from first-principles calculations

A genetic algorithm (GA) coupled with a tight-binding (TB) interatomic potential is used to search for the low-energy structures of medium-sized Ni n (n = 36-40) clusters. Structural candidates obtained from our GA search are further optimized with first-principles calculations. The medium-sized nickel clusters ranging from 36 to 40 atoms are found to favor the double-icosahedron-based structures with a Ni7 core (a pentagonal bipyramidal structure) except Ni38 cluster. The lowest-energy structure of Ni38 can be considered to be a magic cluster, which is a typical face-centered cubic structure with large stability and magnetic moment.

Song, W.↗
DOE OSTI2019

First Principles Calculation of the Entropy of Liquid Aluminum

The information required to specify a liquid structure equals, in suitable units, its thermodynamic entropy. Hence, an expansion of the entropy in terms of multi-particle correlation functions can be interpreted as a hierarchy of information measures. Utilizing first principles molecular dynamics simulations, we simulate the structure of liquid aluminum to obtain its density, pair and triplet correlation functions, allowing us to approximate the experimentally measured entropy and relate the excess entropy to the information content of the correlation functions. We discuss the accuracy and convergence of the method.

36 MATERIALS SCIENCE↗
NASA NTRS2016

First-Principles Definition and Measurement of Planetary Electromagnetic-Energy Budget

The imperative to quantify the Earths electromagnetic-energy budget with an extremely high accuracy has been widely recognized but has never been formulated in the framework of fundamental physics. In this paper we give a first-principles definition of the planetary electromagnetic-energy budget using the Poynting- vector formalism and discuss how it can, in principle, be measured. Our derivation is based on an absolute minimum of theoretical assumptions, is free of outdated notions of phenomenological radiometry, and naturally leads to the conceptual formulation of an instrument called the double hemispherical cavity radiometer (DHCR). The practical measurement of the planetary energy budget would require flying a constellation of several dozen planet-orbiting satellites hosting identical well-calibrated DHCRs.

phenomenology↗
DOE OSTI2016

Mechanical and electronic properties of antiperovskite Ti-based compounds AXTi{sub 3} (X = C, N): A first-principles investigation

In this paper, we systematically studied the mechanical and electronic properties of a series of antiperovskite-type Ti-based ternary carbides and nitrides AXTi{sub 3} (A = Ba, Ca, In, Sn, Sr, Zn, Cu, Al, Ga, Cd, and La; X = C, N) from first-principles calculations. By calculating the formation energies, elastic constants, and other mechanical parameters, we predicted that 7 carbides ACTi{sub 3} and 7 nitrides ANTi{sub 3} compounds are stable among the 22 compounds. The predicted large Young's modulus and high hardness imply a good mechanical application prospect of AXTi{sub 3}. Particularly, SnNTi{sub 3} was found to show ferromagnetic ground state. For the electronic structure, our results confirm that the compounds are metallic in nature, and the density of states near the Fermi energy is predominately contributed by Ti-3d states. The effect of A- and X-site atom doping on AXTi{sub 3} can be evaluated by rigid band approximation. Our prediction will be useful for the experimental exploration of the new antiperovskite compounds.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Intrinsic thermal conductivities and size effect of alloys of wurtzite AlN, GaN, and InN from first-principles

Despite the fact the alloys of wurtzite AlN, GaN, and InN are widely used in electronics, the studies on their thermal conductivities (κ) are inadequate, and the intrinsic limits are still unknown. In this work, the intrinsic κ of alloys and their films are calculated from first-principles within the virtual crystal treatment. The κ of alloys are strongly suppressed even by a small amount of alloying. For instance, with only 1% alloying of Al or In, κ of GaN decreases about 60%. At relatively high alloying, with concentration between 0.2 and 0.8, the κ of alloys are not significantly changed. At room temperature, the minimal a-axis κ are about 18, 22, and 8 W m{sup −1} K{sup −1}, while the minimal c-axis κ are about 22, 27, and 10 W m{sup −1} K{sup −1} for Al{sub x}Ga{sub 1−x}N, In{sub x}Ga{sub 1−x}N, and In{sub x}Al{sub 1−x}N, respectively. The size effect in films can persist up to a few tens of micrometers, and κ can be reduced by half in about 100 nm thick films.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

The origin of metallic conductivity in Pt 3 O 4 : a first principles study

The platinum oxide Pt 3 O 4 exhibits metallic conductivity even though it contains square-planar PtO4 units, which in related oxides such as PtO are usually associated with insulating behavior. To identify the electronic origin of this anomalous metallicity, we performed a comprehensive first-principles study using the PBE and r 2 SCAN functionals together with Hubbard U corrections and spin-orbit coupling (SOC). Structural benchmarks show that r 2 SCAN with SOC and a moderate U value (<4 eV) reproduces the experimental lattice constants and formation enthalpy, whereas larger U values (~8 eV) destabilize the cubic structure. Across all functionals and U values considered in this work, Pt 3 O 4 remains metallic. Analyses of the projected density of states, band structures, charge-density isosurfaces, and bonding characteristics demonstrate that the dominant contribution to the metallic character originates from delocalized Pt–O–Pt hybridized antibonding states at the Fermi level. Direct Pt–Pt interactions are present but contribute less strongly to the conductivity. Bader charge analysis reveals only weak Pt charge disproportionation, consistent with mixed Pt II /Pt III character, and a small charge-transfer energy that prevents localization of the Pt 5d electrons even at elevated U. In contrast, PtO develops a Mott or charge-transfer gap under modest U despite having the same PtO 4 coordination environment. These findings demonstrate that persistent Pt–O–Pt covalency is the primary driver of metallicity in Pt 3 O 4 and support the view that this phase can remain conductive under oxygen reduction and oxygen evolution reaction conditions in fuel cell and electrolyzer environments.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Thermal analysis of VCSEL arrays based on first principle theory and finite element method

Al{sub x}Ga{sub 1−x}As is a main epitaxial material of 850-nm VCSEL. In order to analyze lattice match and heat production, the band gap of Al{sub x}Ga{sub 1−x}As was built, using the first-principles calculation theory. In addition, based on thermoelectric coupling three-dimensional (3D) finite element method, details on the surface temperature distributions of different 850-nm VCSEL arrays were analyzed. Array spacing and array form have an effect on heat dissipation of VCSEL arrays. The diamond array with 18 light emitting units shows the best thermal stability among others.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Dynamic mode decomposition of nonequilibrium electron-phonon dynamics: accelerating the first-principles real-time Boltzmann equation

Abstract Nonequilibrium dynamics governed by electron–phonon ( e -ph) interactions plays a key role in electronic devices and spectroscopies and is central to understanding electronic excitations in materials. The real-time Boltzmann transport equation (rt-BTE) with collision processes computed from first principles can describe the coupled dynamics of electrons and atomic vibrations (phonons). Yet, a bottleneck of these simulations is the calculation of e –ph scattering integrals on dense momentum grids at each time step. Here we show a data-driven approach based on dynamic mode decomposition (DMD) that can accelerate the time propagation of the rt-BTE and identify dominant electronic processes. We apply this approach to two case studies, high-field charge transport and ultrafast excited electron relaxation. In both cases, simulating only a short time window of ~10% of the dynamics suffices to predict the dynamics from initial excitation to steady state using DMD extrapolation. Analysis of the momentum-space modes extracted from DMD sheds light on the microscopic mechanisms governing electron relaxation to a steady state or equilibrium. The combination of accuracy and efficiency makes our DMD-based method a valuable tool for investigating ultrafast dynamics in a wide range of materials.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Temperature effects on the energy bandgap and conductivity effective masses of charge carriers in lead telluride from first-principles calculations

We determined the temperature effects on the electronic properties of lead telluride (PbTe) such as the energy bandgap and the effective masses of charge carriers by incorporating the structural changes of the material with temperature using ab-initio density functional theory (DFT) calculations. Though the first-principles DFT calculations are done at absolute zero temperatures, by incorporating the lattice thermal expansion and the distortion of Pb{sup 2+} ions from the equilibrium positions, we could determine the stable structural configuration of the PbTe system at different temperatures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

First-principles study on stability of transition metal solutes in aluminum by analyzing the underlying forces

Although there have been some investigations on behaviors of solutes in metals under strain, the underlying mechanism of how strain changes the stability of a solute is still unknown. To gain such knowledge, first-principles calculations are performed on substitution energy of transition metal solutes in fcc Al host under rhombohedral strain (RS). Our results show that under RS, substitution energy decreases linearly with the increase of outermost d radius r{sub d} of the solute due to Pauli repulsion. The screened Coulomb interaction increases or decreases the substitution energy of a solute on condition that its Pauling electronegativity scale ϕ{sub P} is less or greater than that of Al under RS. This paper verifies a linear relation of substitution energy change versus r{sub d} and ϕ{sub P} under RS, which might be instructive for composition design of long life alloys serving in high stress condition.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Trends of Alkane Activation on Doped Cobalt (II, III) Oxide from First Principles

The surface doping of a metal oxide can tune its catalytic performance, but it remains unclear how the tuning depends on the dopant type and the surface facet. In this report we study doped Co 3 O 4 (1 1 1) and (3 1 1) surface facets using first-principles density functional theory (DFT) to obtain general descriptors for oxygen reactivity (which include vacancy formation energy and hydrogen adsorption energy) and correlate them to ethane C-H activation energy as a measure of the catalytic performance. The periodic trends of the dopants are investigated for a total of 20 dopants, namely, the elements from K to Ge. We find strong linear correlations between the oxygen reactivity descriptors and the computed energy barriers. We also discover a strong surface facet sensitivity among certain dopants such that different surface orientations and sites lead to different or even the opposite dopant performance. This work provides a useful guide for dopant performance in ethane activation on the two very different Co 3 O 4 surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

A first-principle calculation of the XANES spectrum of Cu{sup 2+} in water

The progress in high performance computing we are witnessing today offers the possibility of accurate electron density calculations of systems in realistic physico-chemical conditions. In this paper, we present a strategy aimed at performing a first-principle computation of the low energy part of the X-ray Absorption Spectroscopy (XAS) spectrum based on the density functional theory calculation of the electronic potential. To test its effectiveness, we apply the method to the computation of the X-ray absorption near edge structure part of the XAS spectrum in the paradigmatic, but simple case of Cu{sup 2+} in water. In order to keep into account the effect of the metal site structure fluctuations in determining the experimental signal, the theoretical spectrum is evaluated as the average over the computed spectra of a statistically significant number of simulated metal site configurations. The comparison of experimental data with theoretical calculations suggests that Cu{sup 2+} lives preferentially in a square-pyramidal geometry. The remarkable success of this approach in the interpretation of XAS data makes us optimistic about the possibility of extending the computational strategy we have outlined to the more interesting case of molecules of biological relevance bound to transition metal ions.

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

A prediction of the thermodynamic, thermophysical, and mechanical properties of CrTaO 4 from first principles

It is reported that the self-forming CrTaO 4 oxide scale can protect refractory high-entropy alloys from oxidation, superior to Cr 2 O 3 . In this paper, the phase stability, mechanical, and thermal properties of three polymorphous phases of CrTaO 4 are systematically investigated from first-principles density functional theory calculations. The mechanical properties predicted using the strain–energy methods indicated that all three phases are mechanically stable. The temperature dependence of elastic constants and polycrystalline moduli of three phases demonstrated the thermal softening as temperature increase. The Helmholtz-free energies as a function of volume and temperature are derived from phonon dispersions within the quasi-harmonic approximation at six strained volumes. The calculated apparent bulk coefficients of thermal expansion of these three phases are evaluated, the highest value approximately 13.4× 10 –6 K –1 within a temperature range of 500–2000 K for the rutile I4 1 md phase. The lattice thermal conductivity calculated by the Debye–Callaway model suggested that the rutile type I4 1 md phase has the lowest value of approximately 2.1 W/m/K at 1800 K. The other two phases, C2/m and P2/c, exhibit higher values due to relatively lower Grüneisen parameters and larger phonon velocities. The melting point of CrTaO 4 is predicted to be between 1975 and 2449 K using ab initio molecular dynamics simulations. Finally, this work provides a comprehensive theoretical understanding of the thermodynamic, mechanical, and thermal properties for the new material CrTaO 4 and serves as an example of a viable computational design strategy for improved oxidation resistance of refractory alloys at high temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Grain boundary stability and influence on ionic conductivity in a disordered perovskite -- a first-principles investigation of lithium lanthanum titanate

The origin of ionic conductivity in bulk lithium lanthanum titanate, a promising solid electrolyte for Li-ion batteries, has long been under debate, with experiments showing lower conductivity than predictions. Recent microscopy images show Type I and Type II grain boundaries. Using first-principles based calculations we find that experimentally observed Type I boundaries are more stable compared to the Type II grain boundaries, consistent with their observed relative abundance. Grain boundary stability appears to strongly anti-correlate with the field strength as well as the spatial extent of the space charge region. Ion migration is faster along Type II grain boundaries than across, consistent with recent experiments of increased conductivity when Type II densities were increased.

36 MATERIALS SCIENCE↗
DOE OSTI2015

First-principles calculations of phonons and Raman spectra in monoclinic CsSnCl 3

Density functional perturbation theory is used here to calculate the phonons at the zone center for monoclinic CsSnCl 3 . Furthermore, we report the calculated normal mode frequencies classified according to irreducible representations for both infrared-active and Raman-active modes. We also report the dielectric constants and Born-effective charges and investigate the anisotropy of the nonanalyticities near the zone center. The first-principles calculated Raman-active phonon frequencies and simulated Raman spectra are compared with experimental results from literature. We find that aside from the first-order allowed Raman modes of A g and B g symmetries, forbidden LO Raman modes appear prominently in the measured spectra. Several of these modes are close to or coincide with allowed modes and alter their intensity, while others appear as separate otherwise unexplained peaks. With this interpretation, good agreement is obtained with experimental mode frequencies to within a few cm -1 .

36 MATERIALS SCIENCE↗
DOE OSTI2018

Ocean of Data: Integrating First-Principles Calculations and CALPHAD Modeling with Machine Learning

Thermodynamics is a science concerning the state of a system, whether it is stable, metastable or unstable, when interacting with the surroundings. Computational thermodynamics enables quantitative calculations of thermodynamic properties as a function of both external conditions and internal configurations, in terms of first and second derivatives of energy with respect to either potentials or molar quantities. Thermodynamic modeling based on the CALPHAD method enables the thermodynamics beyond stable states and is the foundation of Materials Genome and materials design. In last several decades, first-principles calculations based on density functional theory have provided invaluable thermochemical data to improve the robustness of CALPHAD modeling. Today with ever increasing computing power and large amount of data repositories online, it calls for a new paradigm for CALPHAD modeling approach incorporating machine learning to create a sustainable ecosystem for the ocean of data and for emergent behaviors.

Chemistry↗
DOE OSTI2021

Structure sensitivity of ammonia electro-oxidation on transition metal surfaces: A first-principles study

Ammonia electro-oxidation is a promising catalytic reaction for application in alkaline fuel cells. In this paper we study the trends in this reaction on the (1 0 0) facet of eight fcc transition metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh. We calculate from first-principles (DFT-GGA-PW91) the energetics for two mechanisms: (i) the N + N mechanism and (ii) the Gerischer-Mauerer mechanism. The onset potentials for both mechanisms are provided for both (1 0 0) and (1 1 1) facets. We also calculate the activation energies for the N-N bond-making non-Faradaic events on Cu, Pt, Pd, Ni, Ir, and Rh. We discover that N* – which is considered a poison for Pt(1 1 1) – is a reactive intermediate on Pt(1 0 0), allowing for a facile dimerization to N2 on Pt(1 0 0) at high potentials. We draw similar analyses for the structure sensitivity on the other metals, and we conclude with some general principles to guide catalyst design for this reaction.

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

Machine Learning-Accelerated First-Principles Molecular Dynamics Reveals C–C Coupling Mechanisms toward Ethylene on Cu(100)

Here, the Cu(100) termination has been identified as the most effective facet for converting CO and CO 2 into ethylene. To enhance both the activity and selectivity of ethylene production, we perform machine-learning-accelerated, first-principles molecular dynamics simulations at 298 K in an explicit solvent at pH 7 to elucidate the C–C coupling mechanism─the critical reaction step in forming C 2+ products. Among the six potential C–C coupling pathways, the most feasible are CO* dimerization and CO – CHO* and CHO* – CHO* couplings. Using the computational hydrogen electrode method, we demonstrate that all three pathways are equally accessible at −0.6 V vs RHE. At a potential below −1.0 V vs RHE, the thermodynamic barriers for the CO – CHO* and CHO* – CHO* pathways become negligible. Our computational findings explain the experimental observations, particularly the absence of C 2+ products above −0.4 V vs RHE and the peaks in ethylene production near −0.6 and −1.0 V vs RHE. Since CHO* acts as a key intermediate common to both C–C coupling and CH 4 formation, we propose that suppressing CHO* hydrogenation would inhibit CH 4 pathways, thereby maximizing ethylene selectivity.

CO2 reduction↗