Search NASA⌕ Search

SEARCH · Search NASA

Results for “ab initio methods”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,423 records · Page 79
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

First principles study of the structural, elastic, electronic and phonon properties of CdX{sub 2}O{sub 4} (X=Al, Ga, In) spinel-type oxides

We have performed ab-initio calculations of the structural, electronic, elastic and dynamical properties for the spinel compounds CdX{sub 2}O{sub 4} (X=Al, Ga, In) using the plane wave pseudo-potential method within the generalized gradient approximation (GGA). The calculated lattice parameters, elastic constants for these compounds are in good agreement with the previous calculated values. The computed direct band gaps of CdAl{sub 2}O{sub 4}, CdGa{sub 2}O{sub 4} and CdIn{sub 2}O{sub 4} are 2.90 eV, 1.92 eV and 1.16 eV, respectively. The lattice vibrations were calculated by direct method. The calculated phonon dispersion curves show that all compounds are dynamically stable in the spinel structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

An optimally tuned range-separated hybrid starting point for ab initio GW plus Bethe–Salpeter equation calculations of molecules

The ab initio GW plus Bethe–Salpeter equation (GW-BSE, where G is the one particle Green's function and W is the screened Coulomb interaction) approach has emerged as a leading method for predicting excitations in both solids and molecules with a predictive power contingent upon several factors. Among these factors are the (1) generalized Kohn–Sham eigensystem used to construct the GW self-energy and to solve the BSE and (2) the efficacy and suitability of the Tamm–Dancoff approximation. Here, we present a detailed benchmark study of low-lying singlet excitations from a generalized Kohn–Sham (gKS) starting point based on an optimally tuned range-separated hybrid (OTRSH) functional. We show that the use of this gKS starting point with one-shot G0W0 and G0W0-BSE leads to the lowest mean absolute errors (MAEs) and mean signed errors (MSEs), with respect to high-accuracy reference values, demonstrated in the literature thus far for the ionization potentials of the GW100 benchmark set and for low-lying neutral excitations of Thiel’s set molecules in the gas phase, without the need for self-consistency. The MSEs and MAEs of one-shot G0W0-BSE@OTRSH excitation energies are comparable to or lower than those obtained with other functional starting points after self-consistency. Additionally, we compare these results with linear-response time-dependent density functional theory (TDDFT) calculations and find GW-BSE to be superior to TDDFT when calculations are based on the same exchange-correlation functional. This work demonstrates tuned range-separated hybrids used in combination with GW and GW-BSE can greatly suppress starting point dependence for molecules, leading to accuracy similar to that for higher-order wavefunction-based theories for molecules without the need for costlier iterations to self-consistency.

McKeon, Caroline A. (ORCID:0000000217373503)↗
DOE OSTI2018

First‐principles study in an inter‐granular glassy film model of silicon nitride

Abstract Based on a previously constructed intergranular glassy film ( IGF ) model for bulk silicon nitride, a large periodic model of 3864 atoms containing 2 grains of different orientations from the main bulk β‐Si 3 N 4 and 2 IGF s was fully relaxed using the ab initio density‐functional theory package VASP . The relaxed structure was then used to calculate the electronic structure, density of states, interatomic bonding, partial charge distribution, and electron localization using the OLCAO method. Analysis of the data focuses on the interfacial regions between bulk β‐Si 3 N 4 and the Si‐O‐N glass layer with different orientations. The total bond order density ( TBOD ) is evaluated in different interfacial and bulk regions. We show minor differences in the internal cohesion between crystalline grains of different facets. However, the overall charges in the bulk crystal grains and in the glassy regions are electropositive which are balanced by the negatively charged interfacial region between the two. The presence of a less rigid glassy layer is the reason for structural flexibility in ceramics without a huge penalty in the steric energy. The optimization of the interfacial structure and bonding via the creation of defective sites is the atomic origin for the existence of the IGF in silicon nitride. The insights obtained from this detailed quantum mechanical analysis of a realistic IGF model are discussed including implications on the strength, fracture toughness, and processing methods. We also discuss the potential applications of our method to other complex materials systems.

Ching, Wai‐Yim↗
DOE OSTI2011

Electronic structure of TiO{sub 2} rutile with oxygen vacancies: Ab initio simulations and comparison with the experiment

The electronic structure of TiO{sub 2} rutile with oxygen vacancies, which is a promising insulator, has been analyzed. The ab initio density functional calculations, as well as the comparative analysis of the results obtained in the {sigma}-GGA spin-polarized generalized approximation and those obtained by the {sigma}-GGA + U method with allowance for Coulomb correlations of d electrons titanium atoms in the Hartree-Fock approximation for the Hubbard model, have been performed. It has been found that the effective electron mass in rutile is anisotropic and there are both light (m{sub e}{sup *} = (0.6-0.8)m{sub 0}, where m{sub 0} is the free-electron mass) and heavy (m{sub e}* > 1m{sub 0}) electrons, whereas holes in rutile are only heavy (m{sub e}* Greater-Than-Or-Slanted-Equal-To 2m{sub 0}). It has been shown that the {sigma}-GGA + U method gives a deep occupied level in the band gap and that an oxygen vacancy in rutile is an electron and hole trap.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Ab initio studies of structural, electronic, optical, elastic and thermal properties of CuGaTe{sub 2}

We have performed ab initio calculations for the structural, electronic, optical, elastic and thermal properties of CuGaTe{sub 2}. In this study, we used an accurate full potential linearized augmented plane wave (FP-LAPW) method to find the equilibrium structural parameters and to compute the full elastic tensors. We report electronic and optical properties with the recently developed density functional of Tran and Blaha. Furthermore, optical features such as dielectric functions, refractive indices, extinction coefficient, optical reflectivity, absorption coefficients, optical conductivities, were calculated for photon energies up to 30 eV. The thermodynamical properties such as Debye temperature, entropy and Gruneisen parameter, bulk modulus and hardness were calculated employing the quasi-harmonic Debye model at different temperatures (0–1000 K) and pressures (0–8 GPa) and the silent results were interpreted. Most of the investigated parameters are reported for the first time.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Transitioning NWChem to the Next Generation of Manycore Machines

The NorthWest Chemistry (NWChem) modeling software is a popular molecular chemistry simulation software that was designed from the start to work on massively parallel processing supercomputers[6, 28, 49]. It contains an umbrella of modules that today includes Self Consistent Field (SCF), second order Mller-Plesset perturbation theory (MP2), Coupled Cluster, multi-conguration selfconsistent eld (MCSCF), selected conguration interaction (CI), tensor contraction engine (TCE) many body methods, density functional theory (DFT), time-dependent density functional theory (TDDFT), real time time-dependent density functional theory, pseudopotential plane-wave density functional theory (PSPW), band structure (BAND), ab initio molecular dynamics, Car-Parrinello molecular dynamics, classical molecular dynamics (MD), QM/MM, AIMD/MM, GIAO NMR, COSMO, COSMO-SMD, and RISM solvation models, free energy simulations, reaction path optimization, parallel in time, among other capabilities[ 22]. Moreover new capabilities continue to be added with each new release.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2016

Ab initio prediction of fast non-equilibrium transport of nascent polarons in SrI 2 : a key to high-performance scintillation [First-principles study of hole polaron formation and migration in strontium iodide]

The excellent light yield proportionality of europium-doped strontium iodide (SrI 2 :Eu) has resulted in state-of-the-art γ-ray detectors with remarkably high-energy resolution, far exceeding that of most halide compounds. In this class of materials, the formation of self-trapped hole polarons is very common. However, polaron formation is usually expected to limit carrier mobilities and has been associated with poor scintillator light-yield proportionality and resolution. Here using a recently developed first-principles method, we perform an unprecedented study of polaron transport in SrI 2 , both for equilibrium polarons, as well as nascent polarons immediately following a self-trapping event. We propose a rationale for the unexpected high-energy resolution of SrI 2 . We identify nine stable hole polaron configurations, which consist of dimerised iodine pairs with polaron-binding energies of up to 0.5 eV. They are connected by a complex potential energy landscape that comprises 66 unique nearest-neighbour migration paths. Ab initio molecular dynamics simulations reveal that a large fraction of polarons is born into configurations that migrate practically barrier free at room temperature. Consequently, carriers created during γ-irradiation can quickly diffuse away reducing the chance for nonlinear recombination, the primary culprit for non-proportionality and resolution reduction. We conclude that the flat, albeit complex, landscape for polaron migration in SrI 2 is a key for understanding its outstanding performance. This insight provides important guidance not only for the future development of high-performance scintillators but also of other materials, for which large polaron mobilities are crucial such as batteries and solid-state ionic conductors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Short-range stabilizing potential for computing energies and lifetimes of temporary anions with extrapolation methods

The energy of a temporary anion can be computed by adding a stabilizing potential to the molecular Hamiltonian, increasing the stabilization until the temporary state is turned into a bound state, and then further increasing the stabilization until enough bound state energies have been collected so that these can be extrapolated back to vanishing stabilization. The lifetime can be obtained from the same data, but only if the extrapolation is done through analytic continuation of the momentum as a function of the square root of a shifted stabilizing parameter. This method is known as analytic continuation of the coupling constant, and it requires—at least in principle—that the bound-state input data are computed with a short-range stabilizing potential. In the context of molecules and ab initio packages, long-range Coulomb stabilizing potentials are, however, far more convenient and have been used in the past with some success, although the error introduced by the long-rang nature of the stabilizing potential remains unknown. Here, we introduce a soft-Voronoi box potential that can serve as a short-range stabilizing potential. The difference between a Coulomb and the new stabilization is analyzed in detail for a one-dimensional model system as well as for the {sup 2}Π{sub u} resonance of CO{sub 2}{sup −}, and in both cases, the extrapolation results are compared to independently computed resonance parameters, from complex scaling for the model, and from complex absorbing potential calculations for CO{sub 2}{sup −}. It is important to emphasize that for both the model and for CO{sub 2}{sup −}, all three sets of results have, respectively, been obtained with the same electronic structure method and basis set so that the theoretical description of the continuum can be directly compared. The new soft-Voronoi-box-based extrapolation is then used to study the influence of the size of diffuse and the valence basis sets on the computed resonance parameters.

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

Born effective charges and electric polarization in bulk ε-Fe 2 O 3 : An ab-initio approach

Limitation in the synthesis of single-crystal has restricted the complete understanding of the magnetoelectric properties of bulk ε-Fe 2 O 3 . In order to understand the electric polarization of bulk ε-Fe 2 O 3 , we have employed a first-principles Berry-phase method and the density functional perturbation theory to calculate the spontaneous electric polarization and Born effective charges (BECs) of ε-Fe 2 O 3 . The polarization quanta of the ferroelectric bulk ε-Fe 2 O 3 and its polarization lattice are also reported. The polarization switching through a paraelectric transition phase of a low barrier is found to be favorable. The polarization and BECs calculated by both methods are in good agreement.

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

Energetic and Spectroscopic Properties of Astrophysically Relevant MgC 4 H Radicals Using High-Level Ab Initio Calculations

Considering the importance of magnesium-bearing hydrocarbon molecules (MgC n H; n = 2, 4, and 6) in the carbon-rich circumstellar envelopes (e.g., IRC+10216), a total of 28 constitutional isomers of MgC 4 H have been theoretically investigated using density functional theory (DFT) and coupled-cluster methods. The zero-point vibrational energy corrected relative energies at the ROCCSD(T)/cc-pCVTZ level of theory reveal that the linear isomer, 1-magnesapent-2,4-diyn-1-yl (1, 2 Σ + ), is the global minimum geometry on the MgC 4 H potential energy surface. The latter has been detected both in the laboratory and in the evolved carbon star, IRC+10216. The calculated spectroscopic data for 1 match well with the experimental observations (error ~ 0.78%) which validates our theoretical methodology. Plausible isomerization processes happening among different isomers are examined using DFT and coupled-cluster methods. CASPT2 calculations have been performed for a few isomers exhibiting multireference characteristics. The second most stable isomer, 1-ethynyl-1λ 3 -magnesacycloprop-2-ene-2,3-diyl (2, 2 A 1 , μ = 2.54 D), is 146 kJ mol –1 higher in energy than 1 and possibly the next promising candidate to be detected in the laboratory or in the interstellar medium in future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

The study of disorder and nanocrystallinity in C-S-H, supplementary cementitious materials and geopolymers using pair distribution function analysis

Significant progress was achieved with the application of Rietveld method to characterize the crystalline phases in portland cement paste. However, to obtain detailed information on the amorphous or poorly crystalline phases, it is necessary to analyze the total scattering data. The pair distribution function (PDF) method has been successfully used in the study of liquids and amorphous solids. The method takes the Sine Fourier transform of the measured structure factor over a wide momentum transfer range, providing a direct measure of the probability of finding an atom surrounding a central atom at a radial distance away. The obtained experimental characteristic distances can be also used to validate the predictions by the theoretical models, such as, molecular dynamics, ab initio simulations and density functional theory. The paper summarizes recent results of PDF analysis on silica fume, rice husk ash, fly ash, ASR gel, C-S-H and geopolymers.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Ab Initio Approach and Its Impact on Superconductivity

One of the main motivations for studying superconductivity is to search for high-temperature superconductors, especially room-temperature superconductors. During the long history of more than 100 years since the discovery of superconductivity, a number of high-temperature superconductors were found and several great breakthroughs were achieved. Recently, thanks to advances in computing power, progress in crystal structure prediction, and developments in density functional theory, computations have been carried out to predict the structures and an appearance of superconductivity of hydrides at high pressure. More exciting, it is been the first time when a simple, perfect cubic phase of H{sub 3}S which become superconductor at T{sub c} = 200 K under high pressure was successfully predicted by means of ab initio calculation, and then confirmed experimentally. This observation breaks the temperature record of cuprate with T{sub c} = 164 K and further stimulates the studies of hydrides under pressure. Very recently, the high value of T{sub c} = 286 K was theoretically predicted for LaH{sub 10} at 210 GPa and this prediction has been confirmed experimentally. These two successful examples demonstrate the importance of ab initio approach to superconductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Analysis of phase stability and chemical segregation in the Mo-V alloys using a generalized embedded atom method potential

A new interatomic potential for the Mo-V system is introduced to facilitate the study of phase stability and mechanical properties at lower temperatures. This potential is based on a generalization of the embedded atom method and includes contributions from embedding energy, explicit two- and three-body interactions and nonlocal many-body interaction terms. The parameters of the potential are optimized by using data from ab initio density functional theory (DFT) calculations. The potential is rigorously validated across a range of physical properties, such as elastic constants, equation of states, phonon dispersion curves, point defect properties and melting temperatures for different compositions. Even though our potential is trained on a small dataset, its accuracy is comparable to available machine learning potentials for Mo and V. Furthermore, our results show that an ordered B2 phase is stable at low temperatures in alloys containing 50% V, but the solid solution phase is stable above 800 K. However, such long-range ordering is not observed in V-rich or Mo-rich alloys. In addition, our results show that V segregates to dislocation cores and grain boundaries.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Elucidating structural order and disorder phenomena in mullite-type Al{sub 4}B{sub 2}O{sub 9} by automated electron diffraction tomography

The crystal structure and disorder phenomena of Al{sub 4}B{sub 2}O{sub 9}, an aluminum borate from the mullite-type family, were studied using automated diffraction tomography (ADT), a recently established method for collection and analysis of electron diffraction data. Al{sub 4}B{sub 2}O{sub 9}, prepared by sol-gel approach, crystallizes in the monoclinic space group C2/m. The ab initio structure determination based on three-dimensional electron diffraction data from single ordered crystals reveals that edge-connected AlO{sub 6} octahedra expanding along the b axis constitute the backbone. The ordered structure (A) was confirmed by TEM and HAADF-STEM images. Furthermore, disordered crystals with diffuse scattering along the b axis are observed. Analysis of the modulation pattern implies a mean superstructure (AAB) with a threefold b axis, where B corresponds to an A layer shifted by ½a and ½c. Diffraction patterns simulated for the AAB sequence including additional stacking disorder are in good agreement with experimental electron diffraction patterns. - Graphical abstract: Crystal structure and disorder phenomena of B-rich Al{sub 4}B{sub 2}O{sub 9} studied by automated electron diffraction tomography (ADT) and described by diffraction simulation using DISCUS. - Highlights: • Ab-initio structure solution by electron diffraction from single nanocrystals. • Detected modulation corresponding mainly to three-fold superstructure. • Diffuse diffraction streaks caused by stacking faults in disordered crystals. • Observed streaks explained by simulated electron diffraction patterns.

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

Direct Simulations of H–He Mixtures at Planetary Interior Conditions: Demixing, Insulator–Metal Transition and Miscibility Boundaries

Accurate knowledge of the electrical and thermal conductivities and structural properties of hydrogen–helium mixtures under thermodynamic conditions within and beyond the immiscibility range is very important to predict the thermal evolution and internal structure of gas giant planets like Jupiter and Saturn. Here, we propose a novel method to determine the immiscibility boundary accurately without the need for free energy calculations, while providing consistent insights into structural and transport properties of mixtures. We show with direct large-scale ab initio simulations that the insulator–metal transition (IMT) of the hydrogen subsystem is strongly affected by an admixture with a small fraction of helium and occurs at temperatures significantly higher than those of pure hydrogen. At pressures below 150 GPa, the IMT boundary is not related anymore to the H 2 subsystem dissociation, the system remains insulating even after the full dissociation of H 2 molecules and its transition to an H–He mixture. The offset of the IMT in the H–He mixture relative to the dissociation region in the hydrogen subsystem and the significant reduction of static electrical and thermal conductivity by a factor between two and a few thousand relative to pure hydrogen found in mixtures have consequences for Jupiter and Saturn’s thermal evolution, internal structure, and dynamo action, affecting a large fraction of the interior of both planets.

Helium↗
DOE OSTI2016

Acceleration of saddle-point searches with machine learning

In atomistic simulations, the location of the saddle point on the potential-energy surface (PES) gives important information on transitions between local minima, for example, via transition-state theory. However, the search for saddle points often involves hundreds or thousands of ab initio force calls, which are typically all done at full accuracy. This results in the vast majority of the computational effort being spent calculating the electronic structure of states not important to the researcher, and very little time performing the calculation of the saddle point state itself. In this work, we describe how machine learning (ML) can reduce the number of intermediate ab initio calculations needed to locate saddle points. Since machine-learning models can learn from, and thus mimic, atomistic simulations, the saddle-point search can be conducted rapidly in the machine-learning representation. The saddle-point prediction can then be verified by an ab initio calculation; if it is incorrect, this strategically has identified regions of the PES where the machine-learning representation has insufficient training data. When these training data are used to improve the machine-learning model, the estimates greatly improve. This approach can be systematized, and in two simple example problems we demonstrate a dramatic reduction in the number of ab initio force calls. We expect that this approach and future refinements will greatly accelerate searches for saddle points, as well as other searches on the potential energy surface, as machine-learning methods see greater adoption by the atomistics community.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Time scaling with efficient time-propagation techniques for atoms and molecules in pulsed radiation fields

We present an ab initio approach to solving the time-dependent Schroedinger equation to treat electron- and photon-impact multiple ionization of atoms or molecules. It combines the already known time-scaled coordinate method with a high-order time propagator based on a predictor-corrector scheme. In order to exploit in an optimal way the main advantage of the time-scaled coordinate method, namely, that the scaled wave packet stays confined and evolves smoothly toward a stationary state, of which the squared modulus is directly proportional to the electron energy spectra in each ionization channel, we show that the scaled bound states should be subtracted from the total scaled wave packet. In addition, our detailed investigations suggest that multiresolution techniques like, for instance, wavelets are the most appropriate ones to represent the scaled wave packet spatially. The approach is illustrated in the case of the interaction of a one-dimensional model atom as well as atomic hydrogen with a strong oscillating field.

74 ATOMIC AND MOLECULAR PHYSICS↗