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Results for “first principles density functional theory”

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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Inducing metallicity in graphene nanoribbons via zero-mode superlattices

The design and fabrication of robust metallic states in graphene nanoribbons (GNRs) are challenging because lateral quantum confinement and many-electron interactions induce electronic band gaps when graphene is patterned at nanometer length scales. Recent developments in bottom-up synthesis have enabled the design and characterization of atomically precise GNRs, but strategies for realizing GNR metallicity have been elusive. Here we demonstrate a general technique for inducing metallicity in GNRs by inserting a symmetric superlattice of zero-energy modes into otherwise semiconducting GNRs. We verify the resulting metallicity using scanning tunneling spectroscopy as well as first-principles density-functional theory and tight-binding calculations. Our results reveal that the metallic bandwidth in GNRs can be tuned over a wide range by controlling the overlap of zero-mode wave functions through intentional sublattice symmetry breaking.

36 MATERIALS SCIENCE↗
DOE OSTI2026

First-principles Study of the Tritium Species Diffusion Across Ni-Zircaloy-4 Getter Interface

Tritium is a critical fuel component for experimental nuclear fusion reactors (like tokamaks), typically used in combination with deuterium. In tritium-producing burnable absorber rods (TPBARs), due to its high lithium density, LiAlO2 is used in the form of an annular ceramic pellet enriched with the Li_6 isotope located between the Zircaloy-4 liner and nickel-plated Zircaloy-4 tritium getter. Employing DFT, we explored the tritium diffusion across the pellet and getter.

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

Composition-property correlations in NiTi-based shape memory alloys from the first principles

Development of shape memory alloys (SMA) has been traditionally accomplished by means of extensive empirical efforts, with a very limited support from phenomenological models and related tools. We present a theoretical framework based on the Hamiltonian formalism, which connects important thermodynamic properties directly to the relative energies (the eigenvalues of the Hamiltonian), computed from the first principles using density functional theory. The estimates based on this formalism allow to establish correlations between composition and physical properties, such as relative energies, phase transition temperatures, hysteresis, thermal expansion, and other thermodynamic information. Importantly, estimates and correlations not only provide a fast answer, but also elucidate underpinning of thermodynamic features in terms of the electronic structure. Using this framework, we consider phase transformations and correlations between the selected properties and composition in the NiTi-based ternary and multicomponent shape memory alloys. Our theoretical guidance facilitates design and development of future alloys.

shape memory alloys↗
DOE OSTI2020

Assessing the roles of Cu- and Ag-deficient layers in chalcopyrite-based solar cells through first principles calculations

Chalcopyrites are a demonstrated material platform for realizing efficient thin-film photovoltaics, with the most well known Cu(In,Ga)Se 2 (CIGS)-based solar cells exceeding 23%. Several factors, including flexibility in tuning the absorber bandgap, enhanced surface treatments, and the electrically benign nature of common defects are responsible for the existing high performance and future promise in chalcopyrite-based photovoltaic devices. The introduction of Cu-poor phases (also known as ordered-vacancy compounds or OVCs) between the absorber and buffer layers in CIGS solar cells is known to enhance device performance; however, the overall properties and role of OVCs remain poorly understood. Using first principles calculations based on the density functional theory with screened hybrid functionals, here we explore the electronic structure and stability of OVCs and their band offsets with defect-free chalcopyrite layers in Cu- and Ag-based compounds (ABX 2 where A=Cu, Ag; B=In, Ga, Al; and X=S, Se). Using AB 3 X 5 and AB 5 X 8 stoichiometries as model OVC systems, we report on the variation of the bandgap with the A/B ratio and discuss the trends in other Cu- and Ag-based chalcopyrites beyond CuInSe 2 . We find that the valence and conduction bands are lower in energy in OVCs with respect to the parent ABX 2 chalcopyrite owing to a reduced p–d interaction between X and A atoms. We additionally perform device-level simulations to assess the implications of the results, finding that the valence band offsets of OVCs are favorable, while the conduction band offsets of chalcopyrites beyond CuInSe 2 -based absorbers may be detrimental in conventional solar cell device designs.

14 SOLAR ENERGY↗
DOE OSTI2022

First-Principles Calculations of the Structural, Electronic, Optical, and Mechanical Properties of 21 Pyrophosphate Crystals

Pyrophosphate crystals have a wide array of applications in industrial and biomedical fields. However, fundamental understanding of their electronic structure, optical, and mechanical properties is still scattered and incomplete. In the present research, we report a comprehensive theoretical investigation of 21 pyrophosphates A 2 M (H 2 P 2 O 7 ) 2 •2H 2 O with either triclinic or orthorhombic crystal structure. The molecule H 2 P 2 O 7 is the dominant molecular unit, whereas A = (K, Rb, NH 4 , Tl), M = (Zn, Cu, Mg, Ni, Co, Mn), and H 2 O stand for the cation elements, transition metals, and the water molecules, respectively. The electronic structure, interatomic bonding, partial charge distribution, optical properties, and mechanical properties are investigated by first-principles calculations based on density functional theory (DFT). Most of these 21 crystals are theoretically investigated for the first time. The calculated results show a complex interplay between A, M, H 2 P 2 O 7 , and H 2 O, resulting in either metallic, half-metallic, or semi-conducting characteristics. The novel concept of total bond order density (TBOD) is used as a single quantum mechanical metric to characterize the internal cohesion of these crystals to correlate with the calculated properties, especially the mechanical properties. This work provides a large database for pyrophosphate crystals and a road map for potential applications of a wider variety of phosphates.

36 MATERIALS SCIENCE↗
DOE OSTI2021

First-principles study of electron transport in ScN

We investigate the conduction-band structure and electron mobility in rocksalt ScN based on density functional theory. The first-principles band structure allows us to obtain band velocities and effective masses as a function of energy. Electron-phonon scattering is assessed by explicitly computing the q-dependent electron-phonon matrix elements, with the inclusion of the long-range electrostatic interaction. The influence of free-carrier screening on the electron transport is assessed using the random phase approximation. We find a notable enhancement of electron mobility when the carrier concentration exceeds 10 20 cm -3 . We calculate the room-temperature electron mobility in ScN to be 587 cm2 /Vs at low carrier concentrations. When the carrier concentration is increased, the electron mobility starts to decrease significantly around n = 10 19 cm -3 , and drops to 240 cm 2 /Vs at n = 10 21 cm -3 . We also explore the influence of strain in (111)- and (100)-oriented ScN films. For (111) films, we find that a 1.0% compressive epitaxial strain increases the in-plane mobility by 72 cm 2 /Vs and the out-of-plane mobility by 50 cm 2 /Vs. For (100) films, a 1.0% compressive epitaxial strain increases the out-of-plane mobility by as much as 172 cm2 /Vs, but has a weak impact on the in-plane mobility. Our study sheds light on electron transport in ScN at different electron concentrations and shows how strain engineering could increase the electron mobility.

36 MATERIALS SCIENCE↗
DOE OSTI2020

First-principles calculation of the configurational energy density of states for a solid-state ion conductor with a variant of the Wang and Landau algorithm

In this work, a variant of the Wang and Landau algorithm for calculation of the configurational energy density of states is proposed. The algorithm was developed for the purpose of using first-principles simulations, such as density functional theory, to calculate the partition function of disordered sublattices in crystal materials. The expensive calculations of first-principles methods make a parallel algorithm necessary for a practical computation of the configurational energy density of states within a supercell approximation of a solid-state material. The algorithm developed in this work is tested with the two-dimensional (2d) Ising model to bench mark the algorithm and to help provide insight for implementation to a materials science application. Tests with the 2d Ising model revealed that the algorithm has good performance compared to the original Wang and Landau algorithm and the 1/$\textit{t}$ algorithm, in particular the short iteration performance. Further, a proof of convergence is presented within an adiabatic assumption, and the analysis is able to correctly predict the time dependence of the modification factor to the density of states. The algorithm was then applied to the lithium and lanthanum sublattice of the solid-state lithium ion conductor Li 0.5 La 0.5 TiO 3 . This was done to help understand the disordered nature of the lithium and lanthanum. The results find, overall, that the algorithm performs very well for the 2d Ising model and that the results for Li 0.5 La 0.5 TiO 3 are consistent with experiment while providing additional insight into the lithium and lanthanum ordering in the material. The primary result is that the lithium and lanthanum become more mixed between layers along the c axis for increasing temperature. In part, the simulation of the disordered Li 0.5 La 0.5 TiO 3 system serves as a benchmark for what size systems are currently and in the near future practical to calculate with density functional theory methods.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Phase Stability in U-6Nb Alloy Doped with Ti from the First Principles Theory

First-principles calculations within the density-functional-theory (DFT) approach are conducted in order to explore and explain the effect of small amounts of titanium on phase stability in the U-6Nb alloy. During rapid quenching from high to room temperature, metastable phases α' (orthorhombic), α" (monoclinic), and γ 0 (tetragonal) can form, depending on Nb concentration. Important mechanical properties depend on the crystal structure and, therefore, an understanding of the effect of impurities on phase stability is essential. Insights on this issue are obtained from quantum-mechanical DFT calculations. The DFT framework does not rely on any material-specific assumptions and is therefore ideal for an unbiased investigation of the U-Nb system.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Parameter-free prediction of phase transition in PbTiO 3 through combination of quantum mechanics and statistical mechanics

Thermodynamics of ferroelectric materials and their ferroelectric to paraelectric (FE-PE) transitions is commonly described by the phenomenological Landau theory and more recently by effective Hamiltonian and various potentials, all with model parameters fitted to experimental or theoretical data. Here, in this work, we show that the zentropy theory, which considers the total entropy of a system as a weighted sum of entropies of configurations that the system may experience and the statistical entropy among the configurations, can predict the FE-PE transition without fitting parameters. For PbTiO 3 , the configurations are identified as the FE configurations with 90- or 180° domain walls in addition to the ground state FE configuration without domain wall. With the domain wall energies predicted from first-principles based on density functional theory in the literature as the only inputs, the FE-PE transition for PbTiO 3 is predicted showing remarkable agreement with experiments, unveiling the microscopic fundamentals of the transition.

36 MATERIALS SCIENCE↗
DOE OSTI2024

First-Principles Study on the Role of Cu and Cl-Based Dopants in NiO

Utilization of wide band gap oxide-based materials in thin-film solar energy technologies has increased in recent years. Among the numerous candidate oxide materials, NiO has shown many desirable optoelectronic properties that are applicable to thin-film PV technologies such as cadmium telluride PV. However, one critical factor requiring further investigation is the p-type doping behavior of NiO, specifically when the cadmium telluride solar cell undergoes conventional processes such as copper doping and chlorine-based activation treatment. The previous literature has shown a large degree of variability in hole concentrations in NiO when copper is used as the primary dopant. This study uses first-principles computational modeling based on density functional theory coupled with defect equilibria calculations to quantitatively explore the role of copper and chlorine-based extrinsic dopants in the p-type doping activity of NiO. The study reveals the importance of extrinsic dopants and their binding interactions with nickel vacancies to effectively p-dope NiO. It is suggested that both the formation of V Ni + Cu Ni and V Ni + Cl O defect pairs under a supersaturated state of NiO are potential mechanisms for increasing hole densities. On the other hand, the production of 2Cu Ni severely limits the effectiveness of p-doping in NiO, even in the presence of the aforementioned defect pairs. Furthermore, the study provides a guideline for experimentalists interested in using copper or chlorine species to understand how to controllably p-dope NiO during thin-film synthesis.

chlorine↗
DOE OSTI2020

Self-trapped hole and impurity-related broad luminescence in $β$-Ga 2 O 3

Here we explore the luminescence properties of self-trapped holes and impurity-related acceptors using one-dimensional configuration coordinate diagrams derived from hybrid functional calculations. The photoluminescence spectrum of as-grown $β$-Ga 2 O 3 typically consists of a broad band in the wavelength region from ultraviolet to green and is often dominated by an impurity independent ultraviolet band that is commonly attributed to self-trapped holes. Here, we use the self-trapped hole as a benchmark to evaluate the accuracy of the theoretical defect luminescence spectra and estimate the optical properties of Mg Ga , Be Ga , Ca Ga , Cd Ga , Zn Ga , Li Ga , and N O acceptor impurities, as well as their complexes with hydrogen donors. We also explore $V$ Ga acceptors complexed with hydrogen and Si Ga donor impurities. The results show that these defects can give rise to broad luminescence bands peaking in the infrared to visible part of the spectrum, making them potential candidates for the defect origin of broad luminescence bands in $β$-Ga 2 O 3 .

36 MATERIALS SCIENCE↗
DOE OSTI2021

Exploring metastable states in UO 2 using hybrid functionals and dynamical mean field theory

A detailed exploration of the f-atomic orbital occupancy space for UO2 is performed using a first principles approach based on density functional theory (DFT), employing a full hybrid functional within a systematic basis set. Specifically, the PBE0 functional is combined with an occupancy biasing scheme implemented in a wavelet-based algorithm which is adapted to large supercells. The results are compared with previous DFT + U calculations reported in the literature, while dynamical mean field theory is also performed to provide a further base for comparison. This work shows that the computational complexity of the energy landscape of a correlated f-electron oxide is much richer than has previously been demonstrated. The resulting calculations provide evidence of the existence of multiple previously unexplored metastable electronic states of UO 2 , including those with energies which are lower than previously reported ground states.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Dangling bonds, the charge neutrality level, and band alignment in semiconductors

We present a systematic study of the electronic properties of dangling bonds (DBs) in a variety of semiconductors and examine the relationship between DBs and the charge neutrality level (CNL) in the context of band alignments of semiconductors. We use first-principles calculations based on density functional theory to assess the energetics of DBs in a set of diamond-structure group-IV and III–V or II–VI zinc-blende-structure semiconductors, considering both cation and anion-derived states. We examine the charge-state transition levels of DBs to assess whether they can serve as a CNL to align band structures, by comparing with offsets calculated from interface calculations. Our results show that this approach for evaluating the CNL yields quantitative results for band offsets and provides useful insights. We discuss the relation with alternative approaches for determination of CNLs based on branch-point energies or transition levels of interstitial hydrogen.

36 MATERIALS SCIENCE↗
DOE OSTI2022

First-principles study of quantum defect candidates in beryllium oxide

Beryllium oxide (BeO) is a promising host for quantum defects because of its ultrawide band gap. We conducted comprehensive first-principles investigations of the native point defects in BeO using density functional theory with a hybrid functional. We found that the beryllium and oxygen vacancies are the most stable defects, whereas other native defects such as interstitials or antisites have high formation energies. We investigate the point defects as candidates for quantum defects by examining spin states and internal optical transitions. Here, the oxygen vacancy ($V$$^{+}_{O}$) emerges as a suitable spin qubit or single-photon emitter; we also find its stability can be enhanced by forming a (V O – Li Be ) 0 complex with a Li acceptor. The $O$$^{–}_{Be}$ antisite also has desirable optical and spin properties. Overall, because of its desirable properties as a host material, BeO could be an excellent host for quantum defects, with $V$$^{+}_{O}$, (V O – Li Be ) 0 , and $O$$^{–}_{Be}$ as prime candidates.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Orbital-selective Mott phase and non-Fermi liquid in FePS 3

The layered metal phosphorous trisulfide FePS 3 is reported to be a Mott insulator at ambient conditions and to undergo structural and insulator-metal phase transitions under pressure. However, the character of the resulting metallic states has not been understood clearly so far. Here, we theoretically study the phase transitions of FePS 3 using first-principles methods based on density functional theory and embedded dynamical mean field theory. We find that the Mott transition in FePS 3 can be orbital selective, with t 2g states undergoing a correlation-induced insulator-to-metal transition while e g states remain gapped. We show that this orbital-selective Mott phase, which occurs only when nonhydrostatic pressure is used, is a bad metal (or non-Fermi liquid) with large fluctuating moments due to Hund's coupling. Further application of pressure increases the crystal-field splitting and converts the system to a conventional Fermi liquid with low-spin configurations dominant. Finally, our results show that FePS 3 is an example of a system that realizes an orbital-selective Mott phase, allowing tuning between correlated and uncorrelated metallic properties in an accessible pressure range (≤ 18 GPa).

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Radiative capture rates at deep defects from electronic structure calculations

We present a methodology to calculate radiative carrier capture coefficients at deep defects in semiconductors and insulators from first principles. Electronic structure and lattice relaxations are accurately described with hybrid density functional theory. Calculations of capture coefficients provide an additional validation of the accuracy of these functionals in dealing with localized defect states. We also discuss the validity of the Condon approximation, showing that even in the event of large lattice relaxations the approximation is accurate. We test the method on GaAs:VGa-TeAs and GaN:CN, for which reliable experiments are available, and demonstrate very good agreement with measured capture coefficients.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Topological Dirac Semimetal Phase in Bismuth Based Anode Materials for Sodium-Ion Batteries

Bismuth has recently attracted interest in connection with Na-ion battery anodes due to its high volumetric capacity. It reacts with Na to form Na 3 Bi which is a prototypical Dirac semimetal with a nontrivial electronic structure. Density-functional-theory based first-principles calculations are playing a key role in understanding the fascinating electronic structure of Na 3 Bi and other topological materials. In particular, the strongly-constrained-and-appropriately-normed (SCAN) meta-generalized-gradient-approximation (meta-GGA) has shown significant improvement over the widely used generalized-gradient-approximation (GGA) scheme in capturing energetic, structural, and electronic properties of many classes of materials. Here, we discuss the electronic structure of Na 3 Bi within the SCAN framework and show that the resulting Fermi velocities and s-band shift around the Γ point are in better agreement with experiments than the corresponding GGA predictions. SCAN yields a purely spin-orbit-coupling (SOC) driven Dirac semimetal state in Na 3 Bi in contrast with the earlier GGA results. Our analysis reveals the presence of a topological phase transition from the Dirac semimetal to a trivial band insulator phase in Na 3 Bi x Sb 1-x alloys as the strength of the SOC varies with Sb content, and gives insight into the role of the SOC in modulating conduction properties of Na 3 Bi.

36 MATERIALS SCIENCE↗