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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

First Principles Simulations of Electrified Interfaces in Electrochemistry

This chapter discusses some of the recent advances made in the first principles modeling of electrochemical catalysts. It also discusses the key development, namely the ability to explicitly treat the effects of surface electrification due to electrochemical processes and applied voltages in a computationally efficient manner. The chapter introduces the thermodynamics and statistical mechanics of electrified metal-solution interfaces. It then discusses the structure of the electrode-electrolyte interface and the effects of applied voltages, followed by an overview of the first-principles model and a motivating example. The chapter also provides a brief summary of classical thermodynamics and describes the basics of thermodynamic detour. It considers the thermodynamics of macroscopic systems and introduces several useful fundamental relations. Here, the chapter also considers a system to exist in a certain macrostate, which is a particular thermodynamic state specified by a set of fixed properties such as constant particle number, constant volume, and constant temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Prediction of intrinsic topological superconductivity in Mn-doped GeTe monolayer from first-principles

The recent discovery of topological superconductors (TSCs) has sparked enormous interest. The realization of TSC requires a delicate tuning of multiple microscopic parameters, which remains a great challenge. Here, we develop a first-principles approach to quantify realistic conditions of TSC by solving self-consistently Bogoliubov-de Gennes equation based on a Wannier function construction of band structure, in presence of Rashba spin-orbit coupling, Zeeman splitting and electron-phonon coupling. We further demonstrate the power of this method by predicting the Mn-doped GeTe (Ge 1- x Mn x Te) monolayer—a well-known dilute magnetic semiconductor showing superconductivity under hole doping—to be a Class D TSC with Chern number of -1 and chiral Majorana edge modes. By constructing a first-principles phase diagram in the parameter space of temperature and Mn concentration, we propose the TSC phase can be induced at a lower-limit transition temperature of ~40 mK and the Mn concentration of x ~0.015%. Our approach can be generally applied to TSCs with a phonon-mediated pairing, providing useful guidance for future experiments.

Chemistry↗
DOE OSTI2019

First-principles study of the surface properties of y-LiAlO2: Stability and tritium adsorption

y-LiAlO2 enriched with 6Li isotope exhibits excellent performance under neutron radiation and is used in tritium-producing burnable absorber rods (TPBARs) to produce tritium (T, 3H) in pressurized water reactor (PWR). To better understand the 3H formation and diffusion on the surfaces, the first-principles calculations are performed to study the stability of y-LiAlO2 surface and the 3H adsorption on the surface. By considering all possible symmetrical stoichiometric and nonstoichiometric low-index surfaces, two most stable surfaces, one stoichiometric (100) and one nonstoichiometric (101), were identified. The 3H adsorption and diffusion on the most stable (100) surface were further explored, and the obtained results show that there are four stable sites (three O and one Al atop) for 3H adsorption. The calculated Bader charges of atoms reflect that 3H adsorption on the top of O site is a reduction process, while on the top of Al site is an oxidation one. Under low adsorption coverage of 1/4 per surface unit cell, 3H atoms are adsorbed on the most stable OA atop site. With increasing 3H diffused from bulk to surface, the AlG site is the second choice for 3H adsorption, and then the OB site. The coverage of 2/4 is the most favorable 3H adsorption state due to the counteracted charge transfer. When the coverage is up to 4/4, the interaction between 3H atoms leads to partial formation of T2 molecule that desorbs from surface. Therefore, T2 molecule should be the main product from the perfect surface of y-LiAlO2 at high 3H coverage.

Stability of y-LiAlO2 surface, Tritium-producing b↗
DOE OSTI2024

Machine Learning Accelerated First-Principles Study of the Hydrodeoxygenation of Propanoic Acid

The complex reaction network of catalytic biomass conversions often involves hundreds of surface intermediates and thousands of reaction steps, greatly hindering the rational design of metal catalysts for these conversions. Here, we present a framework of machine learning (ML)-accelerated first-principles studies for the hydrodeoxygenation (HDO) of propanoic acid over transition metal surfaces. The microkinetic model (MKM) is initially parametrized by ML-predicted energies and iteratively improved by identifying the rate-determining species and steps (RDS), computing their energies by density functional theory (DFT), and reparameterizing the MKM until all the RDS are computed by DFT. The Gaussian process (GP) model performs significantly better than the linear ridge regression model for predicting both the adsorption free energies and transition state free energies. Parameterized with energies from the GP model, only 5–20% of the full reaction network has to be computed by DFT for the MKM to possess DFT-level accuracy for the TOF and dominant reaction pathway. While the linear ridge regression model performs worse than the GP model, its performance is greatly improved when only transition states are predicted by the regression model and adsorption energies are computed by DFT. Overall, we find that a high accuracy in adsorption free energies is more important for a reliable MKM than a high accuracy in TS free energies. Lastly, based on the GP model with GOH and GCHCHCO as catalyst descriptors, we build two-dimensional volcano plots in activity and selectivity that can help design promising alloy catalysts for HDO reactions of organic acids.

adsorption↗
DOE OSTI2020

Insights into negative differential resistance in MoS 2 Esaki diodes: A first-principles perspective

MoS 2 is a two-dimensional material with a band gap depending on the number of layers and tunable by an external electric field. The experimentally observed intralayer band-to-band tunneling and interlayer band-to-band tunneling in this material present an opportunity for new electronic applications in tunnel field-effect transistors. However, such a widely accepted concept has yet to be been supported by theoretical investigations based on first principles. In this paper, using density functional theory, in conjunction with nonequilibrium Green's function techniques and our electric field gating method, enabled by a large-scale computational approach, we study the relation between band alignment and transmission in planar and side-stack MoS 2 p–i–n junction configurations. Here, we demonstrate the presence of negative differential resistance for both in-plane and interlayer current, a staple characteristic of tunnel diode junctions, and analyze the physical origin of such an effect. Electrostatic potentials, the van der Waals barrier, and a complex band analysis are also examined for a thorough understanding of Esaki diodes.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

First-Principles Investigation of Electrides Derived from Sodalites

Recently, electride materials, with excess anionic electrons confined in their empty space, have received growing attention due to their promising applications in catalysis, nonlinear optics, and spin electronics. However, the utilization of electride materials is limited by their thermal instability. Here, we introduce an alternative way to achieve the localized anionic electron states via the removal of highly symmetric Wyckoff sites of anions from the existing sodalite compounds. Using four halide sodalites as the parental structures, our simulation reveals that the materials after the removal of anionic halide sites exhibit typical electride behaviors that are characterized by the existence of localized electronic states near the Fermi level. Compared to most previously studied electrides, these materials are expected to be more thermally stable due to the complex structural framework and thus promising for practical applications. Among them, Na 4 (AlSiO 4 ) 3 manifests magnetic electronic structure. We demonstrate that this magnetism originates from a highly localized excess electron state surrounded by electropositive alkaline cations. Here, our results suggest Na 4 (AlSiO 4 ) 3 could be a promising spintronics component, thus encouraging further experimental study.

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 OSTI2019

Alkaline earth ion exchange study in pure silica LTA zeolites using periodic first-principles calculations

Experiments show that Zeolites, such as Linde Type A (LTA), are promising materials for radioactive decontamination processes. In this work, the thermodynamic properties associated with alkaline earth ion (Ca2+, Sr2+ and Ba2+) exchange in pure silica LTA was studied using periodic first-principles calculations. The adsorption energies of alkaline earth ions compared with that of Na+ were investigated. The driving force for the alkaline earth exchange and related isotherms were calculated, and analyzed as a function of the electron chemical potential. The results demonstrate that Na+ in a pure silica LTA can completely be removed by Ba2+ and almost completely be removed by Sr2+ from a stream, but cannot be effectively exchanged by Ca2+. We also showed that electron-donating dopants should suppress the Sr2+ and Ba2+ ion exchange, and that there is a substantial preference for incorporating Ba2+ over Sr2+. Lastly, the substantial difference between the adsorption energies of the ions in an assumed vacuum and those computed in water suggests that a solvation model is needed for accurate representation of ion adsorption in an LTA zeolite.

Kocevski, Vancho↗
DOE OSTI2022

Quantum Confinement and Decoherence Effect on Excited Electron Transfer at the Semiconductor–Molecule Interface: A First-Principles Dynamics Study

Excited electron dynamics at the semiconductor–molecule interface play a vital role in many solar energy conversion applications and beyond. First-principles dynamics simulation is used to study how excited electron dynamics in a type-II semiconductor–molecule interface is affected when the surface of a bulk semiconductor is replaced with that of a quantum dot. In particular, the interface between the hydrogen-terminated silicon(111) surface and a simple organic molecule is investigated. Quantum confinement was found to significantly slow down the excited electron relaxation and the interfacial transfer of the excited electron. Additionally, the role of decoherence was examined. The decoherence affects the dynamics much more significantly for the interface with the quantum dot, while the bulk surface case is affected only marginally by it. Finally, compared to the excited electron relaxation within the quantum dot, the decoherence effect was found to slow down the interfacial transfer from the quantum dot to the molecule by more than an order of magnitude, exhibiting a significant quantum Zeno effect.

charge transfer↗
DOE OSTI2019

Magnetic interactions in BiFeO 3 : A first-principles study

First-principles calculations, in combination with the four-state energy mapping method, are performed to extract the magnetic interaction parameters of multiferroic BiFeO 3 . Such parameters include the symmetric exchange (SE) couplings and the Dzyaloshinskii-Moriya (DM) interactions up to second-nearest neighbors, as well as the single-ion anisotropy (SIA). Here, all magnetic parameters are obtained not only for the R3c structural ground state, but also for the R3m and R¯3c phases in order to determine the effects of ferroelectricity and antiferrodistortion distortions, respectively, on these magnetic parameters. In particular, two different second-nearest-neighbor couplings are identified and their origins are discussed in details. Moreover, Monte Carlo (MC) simulations using a magnetic Hamiltonian incorporating these first-principles-derived interaction parameters are further performed. They result (i) not only in the accurate prediction of the spin-canted G-type antiferromagnetic structure and of the known magnetic cycloid propagating along a < 1¯10 > direction, as well as their unusual characteristics (such as a weak magnetization and spin-density-waves, respectively), (ii) but also in the finding of another cycloidal state of low-energy and that awaits to be experimentally confirmed. Turning on and off the different magnetic interaction parameters in the MC simulations also reveal the precise role of each of them on magnetism.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

The partial reduction of clean and doped alpha-Fe2O3(0001) from first principles

Fe surfaces have a wide range of applications due to the ability of Fe to be present in a number of different oxidation states, which can be further influenced by the presence of dopants that change the energetic and electronic surface properties. Thus, having an understanding of the elementary reduction processes of clean Fe oxide surfaces, and how dopants affect the energetics and electronics of such processes, is crucial to the science-guided design and optimization of said surfaces. In this work, we use density functional theory (DFT) to investigate the partial reduction of a-Fe2O3(0001) in the absence and presence of Pd and Pt dopants. In order to account for the strong on-site Coulombic interactions present in transition metal oxides, we used both the DFT?+?U method and 2006 Heyd-Scuseria-Ernzerhof functional and compare the results obtained from the different methods. We find that oxygen vacancies created in the clean a-Fe2O3(0001) surface prefer to diffuse into a subsurface layer, with the charge left behind from the first surface oxygen vacancy distributing between all of the near surface Fe atoms. The addition of Pd or Pt to the a-Fe2O3(0001) surface significantly decreases the energy required to create the first surface oxygen vacancy, suggesting the dopants intrinsically promote the reduction of a-Fe2O3(0001). Additionally, the presence of the dopants caused the charge left behind by the creation of the first surface oxygen vacancy to be localized on the dopant itself as well as the highest Fe atom. Overall, this work provides insight into the elementary energetic and electronic properties of the fully oxidized and partially reduced a-Fe2O3(0001) surface in the absence and presence of Pd and Pt dopants, which has potential implications for the design and optimization of doped Fe oxide surfaces.

Hensley, Alyssa↗
DOE OSTI2023

First benchmarked electron cooling simulations from first principles

We present the first microscopic electron cooling simulations from first principles with accurate prediction of cooling time. These simulations were performed using our previously developed numerical method, PHAD, which is the first efficient large-scale collisional numerical method in beam physics. The simulation results are benchmarked with the experimental data of the low energy bunched electron cooling of ion beams at the storage ring CSRm at the IMP facility in China. Here, we have accurately considered the nonlinear dynamics in the whole accelerator system in addition to the electron cooling section. As a result, our simulations correctly reproduced cooling times of the experiments from first principles and without any tuning or fitting parameters in the code.

43 PARTICLE ACCELERATORS↗