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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

First-Principles Simulations Correlating X-ray Absorption Spectroscopy Features to Point Defects in h -BN

Hexagonal boron nitride (h-BN) is a promising material for a range of emerging applications in electronics, quantum information technology, and energy storage. Soft X-ray absorption spectroscopy (XAS) is powerful to reveal atomic details of BN, especially in the presence of defects. However, correlating XAS spectral features with specific defect types remains elusive. In this Letter, we report B K-edge XAS measurements of sputter-deposited turbostratic h-BN films and use a combination of first-principles spectroscopic simulations and analysis of detailed electronic structure and local charge transfer characteristics to elucidate their unique spectroscopic features. Our results show that the two main defect-related peaks, between the main π* resonances of h-BN and B2O3, as typically observed in BN films deposited by energetic condensation or bombarded with energetic ions, are associated with electronic states of H-passivated B atoms bonded to one and two oxygen impurity atoms, respectively. These conclusions hold significant implications for applications relying on defect-mediated properties of h-BN.

chemical structure↗
NASA NTRS2022

First-Principles Theory of the Rate of Magnetic Reconnection in Magnetospheric and Solar Plasmas

The rate of magnetic reconnection is of the utmost importance in a variety of processes because it controls, for example, the rate energy is released in solar flares, the speed of the Dungey convection cycle in Earth’s magnetosphere, and the energy release rate in harmful geomagnetic substorms. It is known from numerical simulations and satellite observations that the rate is approximately 0.1 in normalized units, but despite years of effort, a full theoretical prediction has not been obtained. Here, we present a first-principles theory for the reconnection rate in non-relativistic electron-ion collisionless plasmas, and show that the same prediction explains why Sweet-Parker reconnection is considerably slower. The key consideration of this analysis is the pressure at the reconnection site (i.e., the x-line). We show that the Hall electromagnetic fields in antiparallel reconnection cause an energy void, equivalently a pressure depletion, at the x-line, so the reconnection exhaust opens out, enabling the fast rate of 0.1. If the energy can reach the x-line to replenish the pressure, the exhaust does not open out. In addition to heliospheric applications, these results are expected to impact reconnection studies in planetary magnetospheres, magnetically confined fusion devices, and astrophysical plasmas.

Yi-Hsin Liu↗
DOE OSTI2018

Structure and Interaction of Ionic Liquid Monolayer on Graphite from First-Principles

The ionic-liquid/graphite interface is important in understanding the behaviors of the ionic-liquid electrolyte in carbon-based supercapacitors and Li-ion batteries. A row-like cation–anion structure of the 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([BMP][TFSA]) ionic liquid (a popular choice for interfacial studies) on the graphite surface has been suggested on the basis of scanning tunneling microscopy images, but it is unclear if this structure is the most stable one. Herein, we explore alternative models of the [BMP][TFSA] monolayer on graphite basal plane with first-principles density functional theory. We find that the checkerboard type of structure is in fact more stable than the row-like structure. We further use simulated annealing based on classical molecular dynamics simulations to obtain more stable conformations of ions on the surface. Both charge-density-difference and noncovalent-interaction analyses show that the higher stability of the checkerboard structure than the row-like structure is due to the stronger anion–surface interactions in the former. Furthermore, our work therefore suggests a new structure of the [BMP][TFSA] monolayer on the graphite basal plane.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

First-principles theory of the rate of magnetic reconnection in magnetospheric and solar plasmas

Abstract The rate of magnetic reconnection is of the utmost importance in a variety of processes because it controls, for example, the rate energy is released in solar flares, the speed of the Dungey convection cycle in Earth’s magnetosphere, and the energy release rate in harmful geomagnetic substorms. It is known from numerical simulations and satellite observations that the rate is approximately 0.1 in normalized units, but despite years of effort, a full theoretical prediction has not been obtained. Here, we present a first-principles theory for the reconnection rate in non-relativistic electron-ion collisionless plasmas, and show that the same prediction explains why Sweet-Parker reconnection is considerably slower. The key consideration of this analysis is the pressure at the reconnection site (i.e., the x-line). We show that the Hall electromagnetic fields in antiparallel reconnection cause an energy void, equivalently a pressure depletion, at the x-line, so the reconnection exhaust opens out, enabling the fast rate of 0.1. If the energy can reach the x-line to replenish the pressure, the exhaust does not open out. In addition to heliospheric applications, these results are expected to impact reconnection studies in planetary magnetospheres, magnetically confined fusion devices, and astrophysical plasmas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Thermal fluctuations and carrier localization induced by dynamic disorder in MAPbI 3 described by first-principles based tight-binding model

Halide perovskites are strongly influenced by large amplitude anharmonic lattice fluctuations at room temperature. We develop a tight binding model for dynamically disordered MAPbI$_3$ based on density functional theory (DFT) calculations to calculate electronic structure for finite temperature crystal structures at the length scale of thermal disorder and carrier localization. The model predicts individual Hamiltonian matrix elements and band structures with high accuracy, owing to the inclusion of additional matrix elements and descriptors for non-Coulombic interactions. We apply this model to electronic structure at length and time scales inaccessible to first principles methods, finding an increase in band gap, carrier mass, and the sub-picosecond fluctuations in these quantities with increasing temperature as well as the onset of carrier localization in large supercells induced by thermal disorder at 300 K. Finally, we identify the length scale $L^*= 5$ nm as the onset of localization in the electronic structure, associated with associated with decreasing band edge fluctuations, increasing carrier mass, and Rashba splitting approaching zero.

36 MATERIALS SCIENCE↗
NASA NTRS2017

A First-Principles Model Based on Saturation of the Electron Cyclotron Drift Instability for Electron Transport in Hydrodynamics Simulations of Hall Thruster Plasmas

We present a computational model based on the hypothesis that the higher-than-expected electron mobility across magnetic field lines observed in Hall thrusters is due to the growth and eventual saturation of the electron cyclotron drift instability. The key improvement of this model with respect to previous work is that it decouples the saturation of the instability from the correlation that exists between mobility and magnitude of the wave perturbations in linear theory, thereby enabling first-principles simulations. The model has been incorporated in the 2-D (r-z) multi-fluids code Hall2De and simulations of the H6 thruster at 300 V, 20 A are numerically stable and achieve a steady-state solution at a computational cost that is not significantly higher than previous Hall2De simulations. The computed location of the acceleration region is found to be within 10% of the length of the acceleration channel compared to that inferred by experiments. The simulations also capture well the plasma gradients along the channel centerline of this thruster. To further establish the validity of this model, we plan to conduct simulations of other thrusters and/or operating conditions.

Lopez Ortega, Alejandro↗
DOE OSTI2024

First-principles study of hydrogen- and oxygen-related complexes in ScN

Scandium nitride (ScN) is an attractive material for electronic applications due to its high n-type conductivity. Native defects and unintentional impurities may limit its electron concentration and reduce its mobility; therefore, it is important to control their formation and incorporation. Hydrogen and oxygen are unintentional impurities that are commonly present during growth and processing. They act as shallow donors in ScN and hence may be regarded as harmless or even favorable to achieving n-type conductivity. Here we show, using state-of-the-art first-principles calculations, that these impurities can be detrimental because they readily form complexes with scandium vacancies (V Sc ). Isolated V Sc have relatively high formation energies and thus have low concentrations and little impact on electronic properties. However, complexes between V Sc and either hydrogen or oxygen form more readily than the pristine vacancy and will act as both compensating and scattering centers. Our results point to the importance of controlling the incorporation of hydrogen and oxygen in ScN (and AlScN alloys) to avoid degradation of the electronic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Elastic knowledge base of bcc Ti alloys from first-principles calculations and CALPHAD-based modeling

Here, titanium alloys are being investigated as suitable materials for load-bearing implants because of their biocompatibility and mechanical properties. Stress shielding, a common issue with the current load-bearing implant materials, occurs due to a Young’s modulus (E) mismatch between bone (~10–40 GPa) and implants (such as Ti-6Al-4V ~ 110 GPa), which leads to bone dying around the implant and ultimately implant failure. Reducing the Young’s modulus of Ti alloys may overcome the issues of stress shielding and improve implant materials. In the present work, first-principles calculations have been used to predict the single crystal elastic stiffness coefficients (c ij ’s) for the Ti-containing ternary alloys Ti-X-Y(X ≠ Y = Mo, Nb, Sn, Ta, Zr) in the bcc lattice. It is found that the ternary Ti-X-Y (X ≠ Y = Mo, Nb, Ta) alloys behave similarly; so do the ternary Ti-X-Sn (X = Mo, Nb, Ta) alloys and the Ti-X-Zr (X = Mo, Nb, Ta) alloys. This is expected due to the similarity between the Mo, Nb and Ta elements. The results also show that the Ti-Zr-X alloys stabilized the bcc phase at lower alloying concentrations. The polycrystalline aggregate properties are also estimated from the c ij ’s, including bulk modulus, shear modulus and Young’s modulus. The results show that Ti-alloys with compositions close to the bcc stability limit have the lowest E. In combination with previous predictions, a complete elastic database has been established using theCALPHAD (CALculation of PHAse Diagram) based modeling approach. The database results are compared with the E of higher order Ti alloys and shown to be able to predict the E accurately. This complete data-base forms a foundation to tailor Ti alloys for desired elastic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2015

First-Principles Design and Analysis of an Efficient, Pb-Free Ferroelectric Photovoltaic Absorber Derived from ZnSnO 3

Ferroelectric oxides, which exhibit a spontaneous and reversible electric polarization, have recently gained interest for photovoltaic applications, because this polarization can potentially facilitate exciton separation and carrier extraction while also generating open-circuit voltages orders-of-magnitude larger than the band gap. However, photovoltaic efficiencies in these materials are often limited by large band gaps and high hole effective masses. Developing a means to simultaneously reduce both without destroying the ferroelectric polarization could revolutionize photovoltaic technologies. In this work, we use first-principles computations to describe how chemical substitution of oxygen in the recently characterized ferroelectric ZnSnO 3 with sulfur to form ZnSnS 3 reduces the band gap to a near-optimal 1.3 eV while leaving the polarization virtually unchanged. Furthermore, we show that other key photovoltaic materials characteristics, such as hole effective mass, dielectric constant, and absorption coefficient, are also dramatically improved by sulfur substitution. Finally, we demonstrate that the well-known semiconductor GaN provides an excellent substrate on which to grow ZnSnS 3 , forming a strongly bound interface that is free of intrinsic midgap states and exhibits an ideal band alignment for efficient carrier extraction. Finally, this work advances the search for an Earth-abundant, nontoxic, ferroelectric material exhibiting strong solar absorption, and may enable the development of solar cells with both high photovoltage and photocurrent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

First-Principles Study of the Voltage Profile and Mobility of Mg Intercalation in a Chromium Oxide Spinel

The development of Mg batteries, which can potentially achieve higher energy densities than Li-ion systems, is in need of cathodes that can reversibly intercalate Mg 2+ and exhibit a higher energy density than the state-of-the-art Chevrel and thio-spinel cathodes. Recent theoretical and experimental studies indicate that the oxide spinel family presents a set of promising Mg cathodes. Here specifically, in this work, we investigate Mg intercalation into the spinel-MgxCr 2 O 4 system. Using first-principles calculations in combination with a cluster expansion model and the nudged elastic band theory, we calculate the voltage curve for Mg insertion at room temperature and the activation barriers for Mg diffusion, respectively, at different Mg concentrations in the Cr 2 O 4 structure. Our results identify a potential limitation to Mg intercalation in the form of stable Mg-vacancy orderings in the Cr 2 O 4 lattice, which exhibit high migration barriers for Mg diffusion in addition to a steep voltage change. Additionally, we propose cation substitution as a potential mechanism that can be used to suppress the formation of the stable Mg-vacancy ordering, which can eventually enable the practical usage of Cr 2 O 4 as a Mg-cathode.

25 ENERGY STORAGE↗
DOE OSTI2018

First-principles study of surface properties of uranium silicides

We report that uranium silicides are currently under investigation as accident tolerant fuels for light water reactors because of its high uranium density and high thermal conductivity. Surface energy as an important material property is required for modeling of gas bubble behavior in nuclear fuels using mesoscale approaches, such as phase field and rate theory methods. However, there is no such information available for uranium silicides from either experiment or theory. To this end, we study the surface properties of two uranium silicide compounds U 3 Si 2 and U 3 Si using first-principles calculations. Of the low-index facets of tetragonal U 3 Si 2 and U 3 Si, we study a total of 13 surfaces up to a maximum Miller index of 3. From the calculated surface energies, the equilibrium single crystal shapes of U 3 Si 2 and U 3 Si are obtained using Wulff construction. The dominant surface orientation, surface area weighted surface energy and surface anisotropy are predicted. Finally, the obtained surface properties of U 3 Si 2 and U 3 Si can be used for an accurate description of the morphology of fission gas bubbles in uranium silicide fuels in the future.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Effect of pressure on elastic, mechanical and electronic properties of WSe{sub 2}: A first-principles study

Highlights: • B, E and v increase as pressure increases, except for a sudden decrease at 40 GPa. • WSe{sub 2} under pressure has larger shear modulus and higher hardness than WSe{sub 2} at 0 GPa. • WSe{sub 2} has an isostructural semiconductor-semimetal phase transition at 40 GPa. • The covalent bonding between Se and W atoms in the slabs is enhanced under pressure. • The distance of the stacked Se–W–Se slabs is decreased with the increasing pressure. - Abstract: Effect of pressure on elastic, mechanical and electronic properties of WSe{sub 2} has been investigated using the first-principles calculations. The calculated lattice parameters, band structure and elastic constants of WSe{sub 2} at 0 GPa are in good agreement with the available experimental and calculational values. With the increasing pressure, the lattice parameters and volume of WSe{sub 2} decrease whereas the total enthalpy increases. The bulk modulus, Young's modulus and Poisson's ratio of WSe{sub 2} increase with the increasing pressure, except for a sharp decrease at the pressure of 40 GPa. WSe{sub 2} under pressure has larger shear modulus and higher hardness than WSe{sub 2} at 0 GPa. With the increase of pressure, the covalent bonding between Se and W atoms in the slabs is enhanced whereas the distance of the stacked slabs is decreased. Additionally, an isostructural semiconductor-semimetal phase transition of WSe{sub 2} is found to take place at 40 GPa, which is consistent with the experimental observations.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Discrepancy between experimental and theoretical β-decay rates resolved from first principles

The dominant decay mode of atomic nuclei is beta decay (β-decay), a process that changes a neutron into a proton (and vice versa). This decay offers a window to physics beyond the standard model, and is at the heart of microphysical processes in stellar explosions and element synthesis in the Universe1,2,3. However, observed β-decay rates in nuclei have been found to be systematically smaller than for free neutrons: this 50-year-old puzzle about the apparent quenching of the fundamental coupling constant by a factor of about 0.75 (ref. 4) is without a first-principles theoretical explanation. Here, we demonstrate that this quenching arises to a large extent from the coupling of the weak force to two nucleons as well as from strong correlations in the nucleus. We present state-of-the-art computations of β-decays from light- and medium-mass nuclei to 100Sn by combining effective field theories of the strong and weak forces5 with powerful quantum many-body techniques6,7,8. Our results are consistent with experimental data and have implications for heavy element synthesis in neutron star mergers9,10,11 and predictions for the neutrino-less double-β-decay3, where an analogous quenching puzzle is a source of uncertainty in extracting the neutrino mass scale12.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2018

Insight into the optoelectronic properties of designed solar cells efficient tetrahydroquinoline dye-sensitizers on TiO 2 (101) surface: first principles approach

Seven ‘lead’ dye-sensitizers from Tetrahydroquinoline (THQ) family were proposed and designed based on the structural attributes via quantitative-structure property relationship (QSPR) modeling. They were screened rationally through different computational approaches to explore their potential applications as photosensitizers for dye-sensitized solar cells (DSSCs). Compelling photophysical properties such as electron injection driving force, electron injection time, and dye regeneration were studied for the isolated dyes under the DFT and TD-DFT frameworks. Index of spatial extent (S, D, and Δq), the strength of charge transfer and separation along with the charge transfer process is explored. First principle approach including van der Waals density functional calculation of dye@TiO 2 interface indicates that all of the designed dyes have optimal interfacial behavior. Bader charge analysis, partial density of state (PDOS), charge density and electrostatic potential difference calculation confirms that THQ7 and THQ9 are the most efficient dye-sensitizers. The other five designed dyes also possess the required properties to emerge as effective dye-sensitizers potentially better than those already utilized.

14 SOLAR ENERGY↗
DOE OSTI2024

Communication—First-Principles Simulations of LiPF 6 Decomposition in Ethylene Carbonate-Based Electrolytes

We revisit a theoretical result by Okamoto (2013 Journal of The Electrochemical Society , 160 , A404) who calculated the energy barrier for the decomposition of lithium hexafluorophosphate (LiPF 6 ) into LiF + PF 5 when solvated in Ethylene carbonate (EC)-based electrolyte. Using different numerical techniques to discretize the Density Functional Theory (DFT) equations, and different continuum solvation models with the same dielectric constant, our results largely confirm the original calculation. However, simulations with a higher dielectric permittivity value, closer to that of EC, show a lower energy barrier. More importantly, First-Principles simulations with an explicit solvent show a substantially lower energy barrier.

25 ENERGY STORAGE↗
DOE OSTI2019

Ground-State and Thermodynamical Properties of Uranium Mononitride from Anharmonic First-Principles Theory

We report on an advanced density-functional theory (DFT) approach for investigating the ground-state and thermodynamical properties of uranium mononitride (UN). The electronic structure for UN at zero temperature is obtained from DFT that utilizes the generalized gradient approximation (GGA) for the electron exchange and correlation functional and includes spin-orbit interaction and an extension with orbital polarization. Thermodynamical properties are computed within the quasi-harmonic approximation in the Debye–Grüneisen model while anharmonicity is captured in the self-consistent ab initio lattice dynamics (SCAILD) scheme. Anharmonic phonons have heretofore never been modeled from first-principles for UN but they turn out to be important. The computed free energy compares well with that of a CALPHAD (CALculation of PHAse Diagrams) assessment of available experimental data.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

First-Principles Simulations of CuCl in High-Temperature Water Vapor

Experimental data suggest that the solubility of copper in high-temperature water vapor is controlled by the formation of hydrated clusters of the form CuCl(H 2 O) n , where the average number of water molecules in the cluster generally increases with increasing density [Migdisov, A. A.; et al. Geochim. Cosmochim. Acta2014, 129, 33–53]. However, the precise nature of these clusters is difficult to probe experimentally. Moreover, there are some discrepancies between experimental estimates of average cluster size and prior simulation work [Mei, Y. Geofluids2018, 2018, 4279124]. Here, we have performed first-principles Monte Carlo (MC) and molecular dynamics (MD) simulations to explore these clusters in finer detail. We find that molecular dynamics is not the most appropriate technique for studying aggregation in vapor phases, even at relatively high temperatures. Specifically, our MD simulations exhibit substantial problems in adequately sampling the equilibrium cluster size distribution. In contrast, MC simulations with specialized cluster moves are able to accurately sample the phase space of hydrogen-bonding vapors. At all densities, we find a stable, slightly distorted linear H 2 O–Cu–Cl structure, which is in agreement with the earlier simulations, surrounded by a variable number of water molecules. The surrounding water molecules do not form a well-defined second solvation shell but rather a loose network of hydrogen-bonded water with molecular CuCl on the outside edge of the water cluster. We also find a broad distribution of hydration numbers, especially at higher densities. In contrast to previous simulation work but in agreement with experimental data, we find that the average hydration number substantially increases with increasing density. Moreover, the value of the hydration number depends on the choice of cluster definition.

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

First-principles Modeling and Design of Solid-State Interfaces for the Protection and Use of Lithium Metal Anodes

Li-ion batteries are one of the most advanced energy storage technologies in use today. Li-ion batteries are used in a multitude of applications ranging from consumer electronics, medical devices, sensors and grid storage. However, improving the capacity and energy density delivered by current Li-ion technology requires advanced materials research into novel chemical systems. In this project we have focused particularly in the use of solid-state electrolytes with lithium metal electrodes. Research into all solid-state batteries (ASSB) with Li metal electrodes has significantly expanded in recent years, however most studies reported experimental findings, which left substantial room for theoretical and modeling work as a tool to understand and determine design principles allowing reliable and safe use of ASSBs with Li metal. Among the remaining obstacles preventing reliable use of ASSBs with a Li metal electrode, the stability of the interface between the solid electrolyte and Li metal, and the propagation/dendrite formation of Li metal and resulting mechanical degradation of the electrolyte are key phenomenon that are yet to be fully understood. In the current project we have addressed these two coupled phenomena using first principles calculations and mesoscale continuum modeling. We have obtained chemical and electrochemical stability windows for several solid electrolyte materials. Additionally, from mathematical and numerical modeling of Li protrusion and dendrite initiation during plating and stripping we have determined design criteria in terms of chemical, electrochemical, and mechanical properties and operating conditions for which stable deposition can occur. We also considered the effects of mixed electronic-ionic conduction in solid electrolytes, which has more recently been suggested as another important mechanism involved in ASSB failure. Throughout our work we have successfully addressed important questions necessary for the use of ASSB’s. We have determined guiding principles for materials properties and operating conditions necessary to operate ASSB’s. And have proposed novel solid electrolyte materials with predicted chemical stability an ionic conductivity. Although this represents significant progress in our understanding, open questions remain in order to fully develop reliable and safely operate ASSBs with Li metal. Future work, building on this project will require further experimental, theoretical and simulation efforts to address remaining questions.

25 ENERGY STORAGE↗