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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 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Exciton-Defect Interaction and Optical Properties from a First-Principles T-Matrix Approach

Understanding exciton-defect interactions is critical for optimizing optoelectronic and quantum information applications in many materials. However, ab initio simulations of material properties with defects are often limited to high defect density. Here, we study effects of exciton-defect interactions on optical absorption and photoluminescence spectra in monolayer MoS 2 using a first-principles T-matrix approach. We demonstrate that exciton-defect bound states can be captured by the disorderaveraged Green’s function with the T-matrix approximation and further analyze their optical properties. Our approach yields photoluminescence spectra in good agreement with experiments and provides a new, computationally efficient framework for simulating optical properties of disordered 2D materials from firstprinciples.

T-matrix↗
DOE OSTI2018

First-principles study of the α - ω phase transformation in Ti and Zr coupled to slip modes

Here, we present first-principles density functional theory calculations to study the α-ω phase transformation in Ti and Zr and its coupling to slip modes of the two phases. We first investigate the relative energetics of all possible slip systems in the α and ω phases to predict the dominant slip system that is activated during a plastic deformation under an arbitrary load. Using this and the crystallographic orientation relationships between α and ω phases, we construct low energy α/ω interfaces and study the energetics of the slip system at the interface between α and ω to compare to the slip systems in the bulk phases. We find that for a particular crystallographic orientation relationship, where (basal) α ∥ (prismatic–II) ω , and [a] α ∥ [c] ω , the slip at the interface is preferred compared to its bulk counterparts. This implies that the plastically deformed α/ω phase with this orientation relationship prefers to retain the interface (or coexisting phases) than transforming back to the pure phase after unloading. This is consistent with the observation that the ω-phase is retained in samples loaded in flyer plate experiments or under high-pressure torsion. Furthermore, calculation of the energy barrier for α to ω phase transformation as a function of glide at the α/ω interface shows significant coupling between the α-ω phase transformation and slip modes in Ti and Zr.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

A first-principles understanding of point defects and impurities in GaN

Attaining control over the electrical conductivity of gallium nitride through impurity doping is one of the foremost achievements in semiconductor science. Yet, unwanted contaminants and point defects continue to limit device performance, and experimental techniques alone are insufficient for elucidating the behavior of these unintentionally incorporated species. Methodological advancements have made first-principles calculations more powerful than ever and capable of quantitative predictions, though care must still be taken in comparing results from theory and experiment. In this Tutorial, we explain the basic concepts that define the behavior of dopants, unintentional impurities, and point defects in GaN. We also describe how to interpret experimental results in the context of theoretical calculations and also discuss how the properties of defects and impurities vary in III-nitride alloys. Lastly, we examine how the physics of defects and impurities in GaN is relevant for understanding other wide-bandgap semiconductor materials, such as the II–IV-nitrides, boron nitride, and the transition metal nitrides.

36 MATERIALS SCIENCE↗
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 OSTI2017

First-principles investigation of phase stability in the Mg-Sc binary alloy

The recent discovery of shape memory behavior in Mg-Sc alloys has opened the door to the possibility of lightweight shape memory alloys. Very little is known, however, about martensitic phase transformations or about equilibrium phase stability in this alloy system. In this paper we report on a first-principles statistical mechanics study of zero Kelvin and finite temperature phase stability of hcp, bcc, and fcc based phases in the Mg-Sc binary. Our calculations reveal a rich array of phase transitions among the different low-temperature ordered and high-temperature disordered phases. Ground state orderings on hcp, bcc, and fcc belong to families of hierarchical structures containing rods of scandium atoms assembled in layers that repeat periodically. Both fcc and bcc are found to undergo a series of second-order phase transformations with increasing temperature until they completely disorder. A high degree of degeneracy is predicted at low and high temperatures among hcp, bcc, and fcc, a property that is likely to play an important role in the shape memory effects observed in this alloy.

36 MATERIALS SCIENCE↗
DOE OSTI2019

First-principles study of surface properties of crystalline and amorphous uranium aluminides

Surface energy is a crucial material property required for the modeling of fission gas bubble behavior in nuclear materials. However, there is no information available regarding the surface properties of uranium aluminides. In this work we systematically investigate the surface properties of uranium aluminides (UAl 3 and UAl 4 ) by first-principles density functional theory (DFT) calculations. Specifically, a total of 13 surface orientations with a maximum Miller index (MMI) up to 3 are studied for cubic UAl 3 , while 19 surfaces with a MMI of 2 for orthorhombic UAl 4 . Using the surface energies predicted by DFT, the surface properties of equilibrium single crystal UAl 3 and UAl 4 , including surface area weighted surface energy, dominant surface orientations and surface anisotropy, are obtained from Wulff construction. To understand gas bubble behaviors in amorphous uranium aluminides under irradiation, we study the surface properties of amorphous UAl 3 and UAl 4 . Compared to the crystalline phases, the amorphous phases are found to have lower surface energies due to the reduced number of breaking U-Al bonds close to the surface. The currently obtained surface properties of UAl 3 and UAl 4 can be used for the future modeling of gas bubble behaviors in both crystalline and amorphous uranium aluminide fuels.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Structural, elastic, and lattice dynamic stability of yttrium selenide (YSe) under pressure: A first principle study

Structural, elastic, and lattice dynamical stability of YSe has been investigated as a function of pressure through first principles electronic band structure calculations. The comparison of enthalpies of rocksalt type (B1) and CsCl type cubic (B2) structures determined as a function of pressure suggests that the B1 phase will transform to B2 structure at ∼32 (30 GPa at 300 K obtained from comparison of Gibbs free energy at 300 K). The transition is identified to be of first order in nature with a volume discontinuity of ∼6.2% at the transition pressure. Furthermore, the theoretically determined equation of state has been utilized to derive various physical quantities, such as zero pressure equilibrium volume, bulk modulus, and pressure derivative of bulk modulus. The single crystal elastic constants have been predicted at various pressures for both the B1 and B2 structures using the energy strain method. The activation barrier between B1 and B2 phases calculated at transition point is ∼19.7mRy/formula unit. Our lattice dynamic calculations show that both the B1 as well as B2 structures are lattice dynamically stable not only at ambient pressure but also at transition pressure. The B1 phase becomes lattice dynamically unstable at ∼112 GPa, i.e., much beyond the transition pressure. The effect of temperature on volume and bulk modulus of the YSe in B1 phase has also been examined.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

GAtor: A First-Principles Genetic Algorithm for Molecular Crystal Structure Prediction

We present the implementation of GAtor, a massively parallel, first-principles genetic algorithm (GA) for molecular crystal structure prediction. GAtor is written in Python and currently interfaces with the FHI-aims code to perform local optimizations and energy evaluations using dispersion-inclusive density functional theory (DFT). GAtor offers a variety of fitness evaluation, selection, crossover, and mutation schemes. Breeding operators designed specifically for molecular crystals provide a balance between exploration and exploitation. Evolutionary niching is implemented in GAtor by using machine learning to cluster the dynamically updated population by structural similarity and then employing a cluster-based fitness function. Evolutionary niching promotes uniform sampling of the potential energy surface by evolving several subpopulations, which helps overcome initial pool biases and selection biases (genetic drift). The various settings offered by GAtor increase the likelihood of locating numerous low-energy minima, including those located in disconnected, hard to reach regions of the potential energy landscape. The best structures generated are re-relaxed and re ranked using a hierarchy of increasingly accurate DFT functionals and dispersion methods. GAtor is applied to a chemically diverse set of four past blind test targets, characterized by different types of intermolecular interactions. Furthermore, the experimentally observed structures and other low-energy structures are found for all four targets. In particular, for Target II, 5-cyano-3-hydroxythiophene, the top ranked putative crystal structure is a Z' = 2 structure with PT symmetry and a scaffold packing motif, which has not been reported previously.

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

Vacancies and Vacancy-Mediated Self Diffusion in Cr 2 O 3 : A First-Principles Study

Charged and neutral vacancies and vacancy mediated self diffusion in alpha-Cr2O3 were investigated using first principles density functional theory (DFT) and periodic supercell formalism. The vacancy formation energies of charged defects were calculated using the electrostatic finite-size corrections to account for electrostatic interactions between supercells and the corrections for the bandgap underestimation in DFT. Calculations predict that neutral oxygen (O) vacancies are predominant in chromium (Cr)-rich conditions and Cr vacancies with -2 charge state are the dominant defects in O-rich conditions. The charge transition levels of both O and Cr vacancies are deep within the bandgap indicating the stability of these defects. Transport calculations indicate that vacancy mediated diffusion along the basal plane has lower energy barriers for both O and Cr ions. The most favorable vacancy mediated self diffusion processes correspond to the diffusion of Cr ion in 3+ charge state and O ion in 2- state, respectively. Our calculations reveal that Cr triple defects comprised of Cr in octahedral interstitial sites with two adjacent Cr vacancies along the c-axis have a lower formation energy compared to that of charged Cr vacancies. The formation of such triple defects facilitate Cr self diffusion along the c-axis.

Medasani, Bharat (ORCID:0000000220734162)↗
DOE OSTI2018

First-principles calculations and experimental studies of: XYZ 2 thermoelectric compounds: Detailed analysis of van der Waals interactions

First-principles calculations can accelerate the search for novel high-performance thermoelectric materials. However, the prediction of the thermoelectric properties is strongly dependent on the approximations used for the calculations. Here, thermoelectric properties were calculated with different computational approximations ( i.e. , PBE-GGA, HSE06, spin–orbit coupling and DFT-D3) for three layered XYZ 2 compounds (TmAgTe 2 , YAgTe 2 , and YCuTe 2 ). In addition to the computations, the structural, electrical and thermal properties of these compounds were measured experimentally and compared to the computations. Furthermore, an enhanced prediction of the crystal structure and heat capacity was achieved with the inclusion of van der Waals interactions due to more accurate modeling of the interatomic forces. In particular, a large shift of the acoustic phonons and low-frequency optical phonons to lower frequencies was observed from the dispersion-optimized structure. From the phonon dispersion curves of these compounds, the ultralow thermal conductivity in the investigated XYZ 2 compounds could be described by a recent developed minimum thermal conductivity model. Additionally, for the prediction of the electrical conductivity, a temperature-dependent relaxation time was used, and it was limited by acoustic phonons. While HSE06 has only a small influence on the electrical properties due to a computed band gap energy of >0.25 eV, the inclusion of both van der Waals interactions and spin–orbit coupling leads to a more accurate band structure, resulting in better prediction of electrical properties. Furthermore, the experimental thermoelectric properties of YAgTe 2 , TmAg 0.95 Zn 0.05 Te 2 and TmAg 0.95 Mg 0.05 Te 2 were measured, showing an increase in zT of TmAg 0.95 Zn 0.05 Te 2 by more than 35% ( zT = 0.47 ± 0.12) compared to TmAgTe 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

First-principles study of quantum confinement and surface effects on the electronic properties of InAs nanowires

We have used first principles methods to systematically investigate the quantum confinement effect on the electronic properties of zinc-blende (ZB) and wurtzite (WZ) InAs nanowires (NWs) with different orientations and diameters, and compared their electronic properties before and after pseudo-hydrogen passivation. The results show that the calculated carrier effective masses are dependent on the NW diameter, except for [110] ZB NWs, and the hole effective masses of [111] ZB NWs are larger than the electron effective masses when the NW diameter is ≥26 Å. The band alignments of [111] ZB and [0001] WZ NWs reveal that the effect of quantum confinement on the conduction bands is greater than on the valence bands, and the position of the valence band maximum level changes little with increasing NW diameter. The pseudo-hydrogen passivated NWs have larger band gaps than the corresponding unpassivated NWs. The carrier effective masses and mobilities can be adjusted by passivating the surface dangling bonds.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

Thermoelectric properties of AgSbTe₂ from first-principles calculations

The structural, electronic, and transport properties of AgSbTe₂ are studied by using full-relativistic first-principles electronic structure calculation and semiclassical description of transport parameters. The results indicate that, within various exchange-correlation functionals, the cubic Fd3⁻m and trigonal R3⁻m structures of AgSbTe₂ are more stable than two other considered structures. The computed Seebeck coefficients at different values of the band gap and carrier concentration are accurately compared with the available experimental data to speculate a band gap of about 0.1–0.35 eV for AgSbTe₂ compound, in agreement with our calculated electronic structure within the hybrid HSE (Heyd-Scuseria-Ernzerhof) functional. By calculating the semiclassical Seebeck coefficient, electrical conductivity, and electronic part of thermal conductivity, we present the theoretical upper limit of the thermoelectric figure of merit of AgSbTe₂ as a function of temperature and carrier concentration.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Local strain effect on the band gap engineering of graphene by a first-principles study

We have systematically investigated the effect of local strain on electronic properties of graphene by first-principles calculations. Two major types of local strain, oriented along the zigzag and the armchair directions, have been studied. We find that local strain with a proper range and strength along the zigzag direction results in opening of significant band gaps in graphene, on the order of 10{sup −1 }eV; whereas, local strain along the armchair direction cannot open a significant band gap in graphene. Our results show that appropriate local strain can effectively open and tune the band gap in graphene; therefore, the electronic and transport properties of graphene can also be modified.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2017

Determination of gaseous fission product behavior near the cerium dioxide Σ 3 (111)/[1 1 ¯ 0] tilt grain boundary via first-principles study

We present that grain boundaries (GBs) are the most abundant structural defects in nanostructured nuclear fuels and play an important role in determining fission product behavior, which further affects the performance of nuclear fuels. In this work, cerium dioxide (CeO 2 ) is used as a surrogate material for mixed oxide fuels to understand gaseous fission product behavior, specifically Xe. First-principles calculations are employed to comprehensively study the behavior of Xe and trap sites for Xe near the Σ 3 (111)/[1 1 ¯ 0] grain boundary in CeO 2 , which will provide guidance on overall trends for Xe stability and diffusion at grain boundaries vs in the bulk. Significant segregation behavior of trap sites, regardless of charge states, is observed near the GB. This is mainly ascribed to the local atomic structure near the GB, which results in weaker bond strength and more negative segregation energies. For Xe, however, the segregation profile near the GB is different. Our calculations show that, as the size of trap sites increases, the segregation propensity of Xe is reduced. In addition, under hyper-stoichiometric conditions, the solubility of Xe trapped at the GB is significantly higher than that in the bulk, suggesting higher Xe concentration than that in the bulk. The results of this work demonstrate that the diffusion mechanism of Xe in CeO 2 is comparable to that in UO 2 . The diffusion activation energies of Xe atoms in the Σ3GB are lower than that in the bulk CeO 2 . Lastly, these results suggest that the diffusivity of Xe atoms is higher along the GB than that in the bulk, which enhances the aggregation of Xe atoms near the GB.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Chemical partitioning for the Co--Pr system: First-principles, experiments and energetic calculations to investigate the hard magnetic phase

Co 5 Pr-D2 d is promising permanent magnet. Due to its peritectic formation feature, there is a synthetic challenge to produce single Co 5 Pr-D2 d phase. The object of our study is to assess thermodynamic pathways for crystalline phases under far-from-equilibrium conditions by combining first-principles calculations and experimental measurements into a robust description of the thermodynamic behavior. The energetic calculations, temperature and time dependent phase selections are predicted under varying degrees of chemical partitioning. Our calculation to assess the chemical partitioning-temperatures indicates that the major magnetic compounds: Co 17 Pr 2 -α, Co 5 Pr-D2 d , Co 19 Pr 5 -β, and Co 7 Pr 2 -χ form from a congruent manner to eutectic reactions with decreasing cooling rate. The compositions of the compounds from these highly driven liquids can be far from equilibrium.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Lithiation-enhanced charge transfer and sliding strength at the silicon-graphene interface: A first-principles study

The application of silicon as ultrahigh capacity electrodes in lithium-ion batteries has been limited by a number of mechanical degradation mechanisms including fracture, delamination and plastic ratcheting, as a result of its large volumetric change during lithiation and delithiation. Graphene coating is one feasible technique to mitigate the mechanical degradation of Si anode and improve its conductivity. In this paper, first-principles calculations are performed to study the atomic structure, charge transfer and sliding strength of the interface between lithiated silicon and graphene. Our results show that Li atoms segregate at the (lithiated) Si-graphene interface preferentially, donating electrons to graphene and enhancing the interfacial sliding resistance. Moreover, the interfacial cohesion and sliding strength can be further enhanced by introducing single-vacancy defects into graphene. These findings provide insights that can guide the design of stable and efficient anodes of silicon/graphene hybrids for energy storage applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

First-principles study of magnetic states and the anomalous Hall conductivity of M Nb 3 S 6 ( M = Co, Fe, Mn, and Ni)

Here, inspired by the observation of the extremely large anomalous Hall effect in the absence of applied magnetic fields or uniform magnetization in CoNb 3 S 6 [Nat. Commun. 9, 3280 (2018); Phys. Rev. Research 2, 023051 (2020)], we perform a first-principles study of this and related compounds of the MNb 3 S 6 type with different transition metal M ions to determine their magnetic orders and the anomalous Hall conductivity (AHC). We find that noncoplanar antiferromagnetic ordering is favored relative to collinear or coplanar order in the case of M = Co, Fe, and Ni, while ferromagnetic ordering is favored in MnNb 3 S 6 at low temperatures. The AHC in these materials with noncoplanar spin ordering can reach about e 2 /h per crystalline layer, while being negligible for coplanar and collinear cases. We also find that the AHC depends sensitively on doping and reaches a maximum for intermediate values of the local spin exchange potential between 0.3 and 0.8 eV. Our AHC results are consistent with the reported Hall measurements in CoNb 3 S 6 and suggest a possibility of similarly large anomalous Hall effects in related compounds.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗