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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 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

SEI Formation and Lithium-Ion Electrodeposition Dynamics in Lithium Metal Batteries via First-Principles Kinetic Monte Carlo Modeling

The stabilization and enhanced performance of lithium metal batteries (LMBs) depend on the formation and evolution of the Solid Electrolyte Interphase (SEI) layer as a critical component for regulating the Li metal electrodeposition processes. This study employs a first-principles kinetic Monte Carlo (kMC) model to simulate the SEI formation and Li + electrodeposition processes on a lithium metal anode, integrating both the electrochemical electrolyte reduction reactions and the diffusion events giving place to the SEI aggregation processes during battery charge and discharge processes. The model replicates the competitive interactions between organic and inorganic SEI components, emphasizing the influence of the cycling regime. Results indicate that grain boundaries within the SEI facilitate faster lithium-ion transport compared to crystalline regions, crucial for improving the performance and stability of LMBs. The findings underscore the importance of dynamic SEI modeling for further development of next-generation high-energy-density batteries.

25 ENERGY STORAGE↗
DOE OSTI2015

Temperature-dependence of structural and mechanical properties of TiB{sub 2}: A first principle investigation

High temperature mechanical and thermodynamic properties of TiB{sub 2} are important to its applications as ultrahigh temperature ceramic, which were not well understood. In this study, the thermodynamic and mechanical properties of TiB{sub 2} were investigated by the combination of first principle and phonon dispersion calculations. The thermal expansion of TiB{sub 2} was anisotropic, α{sub c}/α{sub a} is nearly constant (1.46) from 300 K to 1500 K, theoretically. The origination of this anisotropy is the anisotropic compressibility. The heat capacity at constant pressure was estimated from the theoretical entropy and fitted the experimental result quite well when higher-order anharmonic effects were considered. Theoretical isentropic elastic constants and mechanical properties were calculated and their temperature dependence agreed with the existed experiments. From room temperature to 1500 K, the theoretical slope is −0.0211 GPa·K{sup −1}, −0.0155 GPa·K{sup −1}, and −0.0384 GPa·K{sup −1} for B, G, and E, respectively. Our theoretical results highlight the suitability of this method in predicting temperature dependent properties of ultrahigh temperature ceramics and show ability in selecting and designing of novel ultrahigh temperature ceramics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Adsorption Properties of p -Methyl Red Monomeric-to-Pentameric Dye Aggregates on Anatase (101) Titania Surfaces: First-Principles Calculations of Dye/TiO 2 Photoanode Interfaces for Dye-Sensitized Solar Cells

The optical and electronic properties of dye aggregates of p-methyl red on a TiO2 anatase (101) surface were modeled as a function of aggregation order (monomer to pentameric dye) via first principles calculations. A progressive red-shifting and intensity increase toward the visible region in UV/vis absorption spectra is observed from monomeric-to-tetrameric dyes, with each molecule in a given aggregate binding to one of the four possible TiO2 (101) adsorption sites. The pentamer exhibits a blue-shifted peak wave- length in the UV/vis absorption spectra and less absorption intensity in the visible region in comparison; a corresponding manifestation of H-aggregation occurs since one of these five molecules cannot occupy an adsorption site. This finding is consistent with experiment. Calculated density of states (DOS) and partial DOS spectra reveal similar dye…TiO2 nanocomposite conduction band characteristics but different valence band features. Associated molecular orbital distributions reveal dye-to-TiO2 interfacial charge transfer in all five differing aggregate orders; meanwhile, the level of intramolecular charge transfer in the dye becomes progressively localized around its azo- and electron-donating groups, up to the tetrameric dye/TiO2 species. Dye adsorption energies and dye coverage levels are calculated and compared with experiment. Overall, the findings of this case study serve to aid the molecular design of azo dyes towards better performing DSSC devices wherein they are incorporated. In addition, they provide a helpful example reference for understanding the effects of dye aggregation on the adsorbate…TiO2 interfacial optical and electronic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Interfacial bonding and electronic structure of GaN/GaAs interface: A first-principles study

Understanding of GaN interfacing with GaAs is crucial for GaN to be an effective interfacial layer between high-k oxides and III-V materials with the application in high-mobility metal-oxide-semiconductor field effect transistor (MOSFET) devices. Utilizing first principles calculations, here, we investigate the structural and electronic properties of the GaN/GaAs interface with respect to the interfacial nitrogen contents. The decrease of interfacial N contents leads to more Ga dangling bonds and As-As dimers. At the N-rich limit, the interface with N concentration of 87.5% shows the most stability. Furthermore, a strong band offsets dependence on the interfacial N concentration is also observed. The valance band offset of N7 with hybrid functional calculation is 0.51 eV. The electronic structure analysis shows that significant interface states exist in all the GaN/GaAs models with various N contents, which originate from the interfacial dangling bonds and some unsaturated Ga and N atoms. These large amounts of gap states result in Fermi level pinning and essentially degrade the device performance.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

First-principles calculation of Hubbard U for Terbium metal under high pressure

Abstract Using density functional theory (DFT) and linear response approaches, we compute the on-site Hubbard interaction U of elemental Terbium (Tb) metal in the pressure range ∼ 0–65 GPa. The resulting first-principles U values with experimental crystal structures enable us to examine the magnetic properties of Tb using a DFT+U method. The lowest-energy magnetic states in our calculations for different high-pressure Tb phases—including hcp, α -Sm, and dhcp—are found to be compatible with the corresponding magnetic ordering vectors reported in experiments. The result shows that the inclusion of Hubbard U substantially improves the accuracy and efficiency in modeling correlated rare-earth materials. Our study also provides the necessary U information for other quantum many-body techniques to study Tb under extreme pressure conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Optimal spin-qubit hallmarks of sulfur-vacancy defects in 4H-SiC: Design from first principles

We propose neutral defects in 4H-SiC comprising a silicon vacancy and a sulfur atom dopant substituting a carbon atom as an optically controllable spin qubit with application in quantum computing and quantum telecommunications. According to our state-of-the-art first-principles calculation, the proposed defect possess very promising qubit functionalities. This system once again confirms our hypothesis for the rational design of spin qubits and single-photon emitters. Importantly, the atoms of this system have high-abundance isotopes with zero nuclear spin ensuring high spin-coherence time of the qubit.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Understanding zeolite-catalyzed benzene methylation reactions by methanol and dimethyl ether at operating conditions from first principle microkinetic modeling and experiments

In methanol-to-hydrocarbon chemistry, methanol and dimethyl ether (DME) can act as methylating agents. Therefore, in this paper we focus on the different reactivity of methanol and DME towards benzene methylation in H-ZSM-5 at operating conditions by combining first principles microkinetic modeling and experiments. Methylation reactions are known to follow either a concerted reaction path or a stepwise mechanism going through a framework-bound methoxide. By constructing a DFT based microkinetic model including the concerted and stepwise reactions, product formation rates can be calculated at conditions that closely mimic the experimentally applied conditions. Trends in measured rates are relatively well reproduced by our DFT based microkinetic model. We find that benzene methylation with DME is faster than with methanol but the difference decreases with increasing temperature. At low temperatures, the concerted mechanism dominates, however at higher temperatures and low pressures the mechanism shifts to the stepwise pathway. This transition occurs at lower temperatures for methanol than for DME, resulting in smaller reactivity differences between methanol and DME at high temperature. Finally, our theory-experiment approach shows that the widely assumed rate law with zeroth and first order in oxygenate and hydrocarbon partial pressure is not generally applicable and depends on the applied temperature, pressure and feed composition.

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

First-principles-based kinetic Monte Carlo studies of diffusion of hydrogen in Ni–Al and Ni–Fe binary alloys

The diffusion of dilute hydrogen in fcc Ni–Al and Ni–Fe binary alloys was examined using kinetic Monte Carlo method with input kinetic parameters obtained from first-principles density functional theory. The simulation involves the implementation of computationally efficient energy barrier model that describes the configuration dependence of the hydrogen hopping. The predicted hydrogen diffusion coefficients in Ni and Ni 89.4 Fe 10.6 are compared well with the available experimental data. In Ni–Al, the model predicts lower hydrogen diffusivity compared to that in Ni. Overall, diffusion prefactors and the effective activation energies of H in Ni–Fe and Ni–Al are concentration dependent of the alloying element. Furthermore, the changes in their values are the results of the short-range order (nearest-neighbor) effect on the interstitial diffusion of hydrogen in fcc Ni-based alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2019

First-Principles Prediction of Potentials and Space-Charge Layers in All-Solid-State Batteries

As all-solid-state batteries (SSBs) develop as an alternative to traditional cells, a thorough theoretical understanding of driving forces behind battery operation is needed. We present a fully first-principles-informed model of potential profiles in SSBs and apply the model to the Li/LiPON/Li x CoO 2 system. The model predicts interfacial potential drops driven by both electron transfer and Li + space-charge layers that vary with the SSB’s state of charge. Furthermore, the results suggest a lower electronic ionization potential in the solid electrolyte favors Li + transport, leading to higher discharge power.

25 ENERGY STORAGE↗
DOE OSTI2018

First-Principle Calculations on the Structural, Mechanical, and Electronic Properties of Mn{sub 2}RuSi and Mn{sub 2}RuGe Under Pressure

The second- and third-order elastic constants of the new Inverse Heusler compounds Mn{sub 2}RuZ (Z = Si, Ge) are determined from the first-principle calculations combined with homogeneous deformation methods. In terms of the second- and third- order elastic constants, the effective second-order elastic constants of Mn{sub 2}RuZ (Z = Si, Ge) are also presented. Besides, the pressure dependence of the brittle/ductile properties, elastic anisotropy factor, Young’s modulus, and Debye temperature is further investigated. It is found that both Mn{sub 2}RuSi and Mn{sub 2}RuGe display ductile nature at ground state and Mn{sub 2}RuGe has better ductility than Mn{sub 2}RuSi under different pressures. This phenomenon is improved by the Young’s modulus. Finally, the density of states of Mn{sub 2}RuZ (Z = Si, Ge) under different pressures is also calculated in order to reveal the origin of the effect of pressure on the the ductility of Mn{sub 2}RuZ (Z = Si, Ge).

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Quantifying uncertainties in α -nucleus reaction dynamics informed from first principles

The ab initio symmetry-adapted no-core shell model is a microscopic many-body method which naturally describes challenging collective and clustering features of atomic nuclei. Wave functions and observables computed with realistic nucleon-nucleon forces in this framework are tied to first principles, and are hence well-suited for rigorous uncertainty quantification. We discuss α-deuteron and α- 12 C cluster potentials informed by symmetry-adapted calculations, and propagate uncertainties in the effective binary cluster method as well as those in the nuclear interaction to reaction observables, namely scattering phase shifts, cross sections, partial widths and resonance energies. Here, we find that the overall uncertainties are dominated by those originating in the underlying nuclear force, speaking to the need for tighter constraints on realistic nucleon-nucleon interactions.

Ab initio↗
DOE OSTI2020

Stable Surface Terminations of a Perovskite Oxyhydride from First-Principles

Successful synthesis of some perovskite oxyhydrides and their unique catalytic properties have recently attracted researchers’ attention. However, their surface structure remains unclear. Here we identify stable surface terminations of a prototypical perovskite oxyhydride, BaTiO 2.5 H 0.5 , under catalytically relevant temperatures and pressures by using first-principles thermodynamics based on density functional theory. Five low-index facets, including (100), (010), (210), (011), and (211), and their various terminations for a total of 47 different surfaces have been examined for relative stability at different temperatures (700, 500, 300 K) and gas environments (10 –15 ≤ P O2 ≤ 1 atm, 10–15 ≤ PH2 ≤ 100 atm). The most stable ones are found to be (010)-Ba 2 O 2 , (210)-Ti 2 O 2 , and (211)-Ba 2 O 4 H surface terminations. These polar surfaces are stabilized by charge compensation. This work provides important insights into the stable surfaces of perovskite oxyhydrides for future studies of their catalytic properties.

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

Atomic-Scale Insights into Carbon Dissolution in α-, γ-, and θ-Al 2 O 3 : Phase-dependent Transport Dynamics from First-Principles Calculations

α-Al 2 O 3 exhibits superior carburizing corrosion resistance compared to metastable γ-Al 2 O 3 and θ-Al 2 O 3 phases in high-temperature CO 2 environments, yet its atomic-scale origins remain unclear. Using first-principles density functional theory, we systematically investigate carbon dissolution and diffusion in α-Al 2 O 3 , γ-Al 2 O 3 , and θ-Al 2 O 3 , including the effects of oxygen (O) and aluminum (Al) vacancies. Our results show that α-Al 2 O 3 consistently exhibits higher carbon solution enthalpies than γ-Al 2 O 3 and θ-Al 2 O 3 in both pristine and defective structures, indicating lower intrinsic carbon solubility in α-Al 2 O 3 . Vacancies significantly enhance carbon incorporation: O vacancies reduce solution enthalpy, while Al vacancies further amplify this effect, with a strong preference for carbon at Al vacancy sites. Carbon diffusion barriers are also highest in α-Al 2 O 3 , reflecting slower carbon mobility. Al vacancies increase diffusion barriers across all phases, while O vacancies raise barriers in α- and γ-Al 2 O 3 but slightly lower them in θ-Al 2 O 3 . These results reveal a dual mechanism behind the carburizing resistance of α-Al 2 O 3 : reduced carbon solubility and elevated diffusion barriers. Furthermore, this work provides atomic-scale insights to guide the design of alumina-based materials with improved carburizing resistance through phase selection and defect engineering.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Monte Carlo analysis of transient electron transport in wurtzite Zn{sub 1−x}Mg{sub x}O combined with first principles calculations

Transient characteristics of wurtzite Zn{sub 1−x}Mg{sub x}O are investigated using a three-valley Ensemble Monte Carlo model verified by the agreement between the simulated low-field mobility and the experiment result reported. The electronic structures are obtained by first principles calculations with density functional theory. The results show that the peak electron drift velocities of Zn{sub 1−x}Mg{sub x}O (x = 11.1%, 16.7%, 19.4%, 25%) at 3000 kV/cm are 3.735 × 10{sup 7}, 2.133 × 10{sup 7}, 1.889 × 10{sup 7}, 1.295 × 10{sup 7} cm/s, respectively. With the increase of Mg concentration, a higher electric field is required for the onset of velocity overshoot. When the applied field exceeds 2000 kV/cm and 2500 kV/cm, a phenomena of velocity undershoot is observed in Zn{sub 0.889}Mg{sub 0.111}O and Zn{sub 0.833}Mg{sub 0.167}O respectively, while it is not observed for Zn{sub 0.806}Mg{sub 0.194}O and Zn{sub 0.75}Mg{sub 0.25}O even at 3000 kV/cm which is especially important for high frequency devices.

36 MATERIALS SCIENCE↗
DOE OSTI2015

First-principles investigation of thermodynamic, elastic and electronic properties of Al{sub 3}V and Al{sub 3}Nb intermetallics under pressures

The thermodynamic, elastic, and electronic properties of D0{sub 22}-type Al{sub 3}V and Al{sub 3}Nb intermetallics were studied using the first-principle method. The results showed the pressure has profound effects on the structural, mechanical and electronic properties in both Al{sub 3}V and Al{sub 3}Nb. Thermodynamically, the formation enthalpies for Al{sub 3}V and Al{sub 3}Nb were derived, which agreed well with available experimental and theoretical values. Comparably, Al{sub 3}Nb was a more stable phase with the more negative H{sub f} than Al{sub 3}V. Mechanically, the calculated elastic constants showed linearly increasing tendencies, and satisfied the Born's criteria from 0–20 GPa, indicating the mechanically stability of Al{sub 3}V and Al{sub 3}Nb under this pressure range. Further, the mechanical parameters (i.e., bulk modulus (B), shear modulus (G), and Young's modulus (E)) were derived using the Voigt-Reuss-Hill (VRH) method, and in good agreement with available experimental results at the ground state. All these parameters presented the linearly increasing dependences on the external pressure. The B/G ratios and Poisson's ratio indicated that the Al{sub 3}V and Al{sub 3}Nb crystals should exhibit brittle behavior at 0–20 GPa. Additionally, the bulk modulus can be obtained through fitting the Birch-Murnaghan equation (B{sub 0}), computing by VRH method (B{sub H}), and deriving from the elastic theory (B{sub relax}) in both intermetallics. The uniformity of these calculated bulk moduli in each compound exhibited the excellent reliability and self-consistency. In addition, Debye temperature was estimated from the average sound velocity. The Debye temperature showed an increasing dependence on the pressures. Finally, through density of states analysis, Al{sub 3}V and Al{sub 3}Nb were suggested to possess naturally metallic behavior. Under pressures, it was noted that the shapes of peaks and pseudogaps exhibited relative few changes, suggesting Al{sub 3}V and Al{sub 3}Nb has kept structurally stable up to 20 GPa. At zero pressure, Al{sub 3}Nb was considered as a more structurally stable phase with the more number of bonding electrons per atom than Al{sub 3}V. This conclusion was in consistent with the one drawn from the thermodynamic analysis.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

First-principles calculations reveal controlling principles for carrier mobilities in semiconductors

It has long been believed that carrier mobilities in semiconductors can be calculated by Fermi s golden rule (Born approximation). Phenomenological models for scattering amplitudes are typically used for engineering- level device modeling. Here we introduce a parameter-free, first-principles approach based on complex- wavevector energy bands that does not invoke the Born approximation. We show that phonon-limited mobility is controlled by low-resistivity percolation paths and that in ionized-impurity scattering one must account for the effect of the screening charge, which cancels most of the Coulomb tail.Finally, calculated electron mobilities in silicon are in agreement with experimental data.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

First principles study of nearly strain-free Ni/WSe 2 and Ni/MoS 2 interfaces

Metal/transition metal dichalcogenide interfaces are the subject of active research, in part because they provide various possibilities for interplay of electronic and magnetic properties with potential device applications. Here, we present results of our first principles calculations of nearly strain-free Ni/WSe 2 and Ni/MoS 2 interfaces in thin-film geometry. It is shown that while both the WSe 2 and MoS 2 layers adjacent to Ni undergo metallic transition, the layers farther from the interface remain semiconducting. In addition, a moderate value of spin-polarization is induced on interfacial WSe 2 and MoS 2 layers. At the same time, the electronic and magnetic properties of Ni are nearly unaffected by the presence of WSe 2 and MoS 2 , except a small reduction of magnetic moment at the interfacial Ni atoms. Furthermore, these results can be used as a reference for experimental efforts on epitaxial metal/transition metal dichalcogenide heterostructures, with potential application in modern magnetic storage devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

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

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

Song, W.↗