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At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

First-principles theory for Schottky barrier physics

We develop a first-principles theory for Schottky barrier physics. The Poisson equation is solved selfconsistently with the electrostatic charge density over the entire barrier using the density functional theory (DFT) electronic structure converged locally, allowing computation of a Schottky barrier entirely from DFT involving thousands of atomic layers in the semiconductor (SC). Here, the induced charge in the bulk consists of conduction and valence band charges from doping and band bending, as well as charge from the evanescent states in the gap of the SC. The Schottky barrier height (SBH) is determined when the induced charge density and the induced electrostatic potential reach self-consistency. Tests on the GaAs-graphene and Si/Al heterostructures yield SBH, width, along with depletion and inversion layers obtained self-consistently as functions of temperature and bulk doping.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Elastic properties of perovskite ATiO{sub 3} (A = Be, Mg, Ca, Sr, and Ba) and PbBO{sub 3} (B = Ti, Zr, and Hf): First principles calculations

The mechanical properties of perovskite oxides depend on two metal oxide lattices that are intercalated. This provides an opportunity for separate tuning of hardness, Poisson's ratio (transverse expansion in response to the compression), and shear strength. The elastic constants of series of perovskite oxides were studied by first principles approach. Both A-site and B-site cations were systematically varied in order to see their effects on the elastic parameters. To study the effects of A-site cations, we studied the elastic properties of perovskite ATiO{sub 3} for A being Be, Mg, Ca, Sr, or Ba, one at a time. Similarly, for B-site cations, we studied the elastic properties of PbBO{sub 3} for B being Ti, Zr, or Hf, one at a time. The density functional first principles calculations with local density approximation (LDA) and generalized gradient approximation (GGA) were employed. It is found that the maximum C{sub 11} elastic constant is achieved when the atomic size of the cations at A-site and B-site are comparable. We also found that C{sub 12} elastic constant is sensitive to B-site cations while C{sub 44} elastic constant is more sensitive to A-site cations. Details and explanations for such dependencies are discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Exciton Lifetime and Optical Line Width Profile via Exciton–Phonon Interactions: Theory and First-Principles Calculations for Monolayer MoS 2

Exciton dynamics dictates the evolution of photoexcited carriers in photovoltaic and optoelectronic devices. However, interpreting their experimental signatures is a challenging theoretical problem due to the presence of both electron–phonon and many-electron interactions. Here, we develop and apply here a first-principles approach to exciton dynamics resulting from exciton–phonon coupling in monolayer MoS 2 and reveal the highly selective nature of exciton–phonon coupling due to the internal spin structure of excitons, which leads to a surprisingly long lifetime of the lowest-energy bright A exciton. Moreover, we show that optical absorption processes rigorously require a second-order perturbation theory approach, with photon and phonon treated on an equal footing, as proposed by Toyozawa and Hopfield. Such a treatment, thus far neglected in first-principles studies, gives rise to off-diagonal exciton–phonon self-energy, which is critical for the description of dephasing mechanisms and yields exciton line widths in excellent agreement with experiment.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
NASA NTRS2016

Hall2De Simulations with a First-Principles Electron Transport Model Based on the Electron Cyclotron Drift Instability

Several years of work have combined plasma measurements in a laboratory Hall thruster and r-z numerical simulations with Hall2De to isolate the spatial variation of the anomalous collision frequency needed in Ohm’s law to produce the observed thruster behavior. This numerical solution is used here to test the validity of a first-principles model of the anomalous transport in these devices before such model is implemented self-consistently in r-z fluid codes like Hall2De. The first-principles model employs quasi-linear theory and is based on the hypothesis that the Electron Cyclotron Drift Instability (ECDI) excites ion acoustic turbulence that, in turn, enhances the effective collision frequency in these devices. We find that a model of the ECDI that assumes Maxwellian velocity distributions for electrons and singly-charged, main-beam, cold ions (Ti=0.07 eV) is insufficient to explain the expected variation of the anomalous collision frequency both in the interior and exterior of the acceleration channel. When warm ions (~0.5-3 eV) are accounted for, the ECDI model in the channel interior appears more promising but fails by orders of magnitude in the near plume region due to the much higher Landau damping of the ion acoustic waves there. This implies that either (a) some process allows the ECDI instability to remain uninhibited by classical Landau damping or, (b) that a different instability (or instabilities) altogether, also insusceptible to Landau damping, is/are active in this region. A previous hypothesis, that convection of wave energy generated by the ECDI in the channel plays a significant role in the near plume, is not supported by the results of the simulations.

Mikellides, Ioannis G.↗
DOE OSTI2023

Change of Electrical and Transport Properties of Nickel Oxide by Carrier Concentration and Temperature through First-Principle Calculations

Abstract Nickel is typically used as one of the main components in electrical contact devices or connectors. Nickel oxide (NiO) is usually formed on the surfaces of electrodes and can negatively impact system performance by introducing electrical contact resistance. The thermal, electrical, and transport properties of NiO, as a Mott insulator or a p-type semiconductor, can be altered by operating and environmental conditions such as temperature and stress/strain by contact. In this study, we investigate the fundamental material properties of NiO through the first-principle calculations. First, we obtain and compare the lattice parameter, magnetic moment, and electronic structure for NiO via the WIEN2K simulations with four different potentials (i.e., GGA, GGA + U, LSDA, and LSDA + U). Then, using the WIEN2K simulation results with LSDA + U potential that produces a highly accurate bandgap for NiO, we calculate the electrical conductivity and electrical part of the thermal conductivity of nickel and NiO as a function of temperature and carrier concentration through the BoltzTraP simulations. Systematic simulation results revealed that the electrical conductivity relative to the relaxation time for NiO increases with the carrier concentration, while it shows a slightly decreasing trend with temperature under a fixed carrier concentration. By contrast, the electrical part of the thermal conductivity shows an increasing trend considering carrier concentration and temperature.

Shah, Nayem Md. Reza↗
DOE OSTI2024

Comparing first-principles density functionals plus corrections for the lattice dynamics of YBa 2 Cu 3 O 6

The enigmatic mechanism underlying unconventional high-temperature superconductivity, especially the role of lattice dynamics, has remained a subject of debate. Theoretical insights have long been hindered due to the lack of an accurate first-principles description of the lattice dynamics of cuprates. Recently, using the r2SCAN meta-generalized gradient approximation (meta-GGA) functional, we have been able to achieve accurate phonon spectra of an insulating cuprate YBa 2 Cu 3 O 6 and discover significant magnetoelastic coupling in experimentally interesting Cu–O bond stretching optical modes [Ning et al., Phys. Rev. B 107, 045126 (2023)]. We extend this work by comparing Perdew–Burke–Ernzerhof and r2SCAN performances with corrections from the on-site Hubbard U and the D4 van der Waals (vdW) methods, aiming at further understanding on both the materials science side and the density functional side. We demonstrate the importance of vdW and self-interaction corrections for accurate first-principles YBa 2 Cu 3 O 6 lattice dynamics. Since r2SCAN by itself partially accounts for these effects, the good performance of r2SCAN is now more fully explained. Finally, in addition, the performances of the Tao–Mo series of meta-GGAs, which are constructed in a different way from the strongly constrained and appropriately normed (SCAN) meta-GGA and its revised version r2SCAN, are also compared and discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Superconductivity and topological properties of MgB 2 -type diborides from first principles

The superconductivities and topological properties of MgB 2 -type diborides are investigated by means of first-principles calculations with different exchange-correlation functionals. Functionals with the van der Waals (vdW) correction (such as OptB88-vdW) may predict critical temperature (T c ) comparable with experimental results for several MgB 2 -type superconductors, particularly for the pristine MgB 2 (39.3 vs 39 K). Interestingly, the spin-fluctuation is found to play a significant role in the superconducting behavior of diborides with transition metal elements, and their T c can be enhanced monotonically by applying tensile strains. Furthermore, Dirac surface states of Ta B 2 and NbB 2 are revealed, suggesting their potential use as topological superconducting materials. Finally, this paper provides a useful guideline for ab initio studies of superconductivities and topological properties of vdW layered materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

First-principles characterization of the magnetic properties of Cu 2 (OH) 3 Br

Low-dimensional spin-1/2 transition metal oxides and oxyhalides continue to be at the forefront of research investigating nonclassical phases such as quantum spin liquids. In this work, we examine the magnetic properties of the oxyhalide Cu 2 (OH) 3 Br in the botallackite structure using first-principles density functional theory, linear spin-wave theory, and exact diagonalization calculations. This quasi-two-dimensional system consists of Cu 2+ S = 1/2 moments arranged on a distorted triangular lattice. Our exact diagonalization calculations, which rely on a first-principles-based magnetic model, generate spectral functions consistent with inelastic neutron scattering data. By performing computational experiments to disentangle the chemical and steric effects of the halide ions, we find that the dominant effect of the halogen ions is steric in the Cu 2 (OH) 3 X series of compounds.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Excitons and Davydov splitting in sexithiophene from first-principles many-body Green’s function theory

Organic semiconductors have promising and broad applications in optoelectronics. Understanding their electronic excited states is important to help us control their spectroscopic properties and performance of devices. There have been a large amount of experimental investigations on spectroscopies of organic semiconductors, but theoretical calculation from first principles on this respect is still limited. Here, we use density functional theory (DFT) and many-body Green’s function theory, which includes the GW method and Bethe-Salpeter equation, to study the electronic excited-state properties and spectroscopies of one prototypical organic semiconductor, sexithiophene. The exciton energies of sexithiophene in both the gas and bulk crystalline phases are very sensitive to the exchange-correlation functionals used in DFT for ground-state structure relaxation. We investigated the influence of dynamical screening in the electron-hole interaction on exciton energies, which is found to be very pronounced for triplet excitons and has to be taken into account in first principles calculations. In the sexithiophene single crystal, the energy of the lowest triplet exciton is close to half the energy of the lowest singlet one. While lower-energy singlet and triplet excitons are intramolecular Frenkel excitons, higher-energy excitons are of intermolecular charge-transfer type. The calculated optical absorption spectra and Davydov splitting are in good agreement with experiments.

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

Nonlinear electronic excitation in water under proton irradiation: a first principles study

Nonlinear dynamics of electronic excitation bridge physical and physicochemical stages of water radiolysis under proton irradiation, a multi-scale physicochemical process that is fundamental to a wide range of technological and medical applications of high-energy protons. We study the spatial and temporal changes to the excited holes generated in this ionization event using first-principles theory simulation. A significant majority of holes are formed in the immediate vicinity of the irradiating proton paths, and these holes decay rapidly, while secondary excitations are simultaneously induced in regions farther away. While the hole population remains constant, the observed spatially spreading hole distribution cannot be described as concentration-dependent diffusion current. Compared to the primary excitation induced by the irradiating protons, the secondary excitation farther away is somewhat less energetic. Here, the first-principles theory simulation here provides a detailed description of how the primary excitation by proton radiation precedes the formation of cationic holes, which undergo ultrafast chemical processes in water radiolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Using first-principles calculations to screen for fragile magnetism: Case study of LaCrGe 3 and LaCrSb 3

In this study, we present a coupled experimental/theoretical investigation of pressure effect on the ferromagnetism of LaCrGe 3 and LaCrSb 3 compounds. The magnetic, electronic, elastic, and mechanical properties of LaCrGe 3 and LaCrSb 3 at ambient condition are studied by first-principles density-functional theory calculations. The pressure dependences of the magnetic properties of LaCrGe 3 and LaCrSb 3 are also investigated. The ferromagnetism in LaCrGe 3 is rather fragile, with a ferro- to paramagnetic transition at a relatively small pressure (around 7 GPa from our calculations, and 2 GPa in experiments). The key parameter controlling the magnetic properties of LaCrGe 3 is found to be the proximity of the peak of Cr density of states to the Fermi level, a proximity that is strongly correlated with the distance between Cr atoms along the c axis, suggesting that there would be a simple way to suppress magnetism in systems with one-dimensional arrangement of magnetic atoms. By contrast, the ferromagnetism in LaCrSb 3 is not fragile. In conclusion, our theoretical results are consistent with our experimental results and demonstrate the feasibility of using first-principles calculations to aid experimental explorations in screening for materials with fragile magnetism.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Voltage-Dependent First-Principles Barriers to Li Transport within Li-Ion Battery Solid Electrolyte Interphases

Charging a Li-ion battery requires Li-ion transport between the cathode and the anode. This Li-ion transport is dependent on (among other factors) the electrostatic environment that the ion encounters within the solid electrolyte interphase (SEI), which separates the anode from the surrounding electrolyte. A previous first-principles work has illuminated the reaction barriers through likely atomistic SEI environments but has had difficulty accurately reflecting the larger electrostatic potential landscape that an ion encounters moving through the SEI. In this work, we apply the recently developed quantum continuum approximation (QCA) technique to provide an equilibrium electronic potentiostat for first-principles interface calculations. Using QCA, we calculate the potential barrier for Li-ion transport through LiF, Li 2 O, and Li 2 CO 3 SEIs along with LiF–LiF and LiF–Li 2 O grain boundaries, all paired with Li metal anodes. Here, we demonstrate that the SEI potential barrier is dependent on the electrochemical potentials of the anode in each system. Finally, we use these techniques to estimate the change in the diffusion barrier for a Li ion moving in a LiF SEI as a function of the anode potential. We find that properly accounting for interface and electronic voltage effects significantly lowers reaction barriers compared with previous literature results.

25 ENERGY STORAGE↗
DOE OSTI2021

Role of Hydrogen-bonded Bimolecular Formic Acid–Formate Complexes for Formic Acid Decomposition on Copper: A Combined First-Principles and Microkinetic Modeling Study

Hydrogen bonding interactions alter the nanoscale reaction mechanisms of many chemistries. Yet, it remains unclear how they affect heterogeneously catalyzed decomposition of formic acid (FA), a reaction of intense interest since FA is a promising hydrogen carrier. In this work, we elucidate how hydrogen bonding affects the reaction mechanisms for FA decomposition on Cu(111) by combining first-principles density functional theory calculations to calculate reaction energetics, Latin-hypercube sampling to elucidate stable high-coverage adsorbate configurations, and coverage self-consistent mean-field microkinetic models to predict reaction kinetics. We demonstrate that hydrogen-bonded complexes of FA with formate (bimolecular FA–HCOO complexes) can play a dominant role in FA decomposition. Specifically, our first-principles calculations show that hydrogen bonding of FA with HCOO may stabilize the crucial monodentate HCOO intermediate and the transition states for HCOO decomposition, especially at low coverages. We predict that, depending on the reaction conditions, 40–80% of the reaction flux goes through pathways involving the bimolecular FA–HCOO complexes. Additionally, the active site for FA decomposition on Cu(111) involves a high coverage (~0.4 monolayers (ML)) of these complexes, which unexpectedly stabilize intermediates and transition states via van der Waals interactions. Our work provides molecular insights consistent with previous experimental observations on supported Cu/Al 2 O 3 catalysts. This paves the way toward the development of novel catalysts for FA decomposition as well as for other industrially important chemistries with intermediates capable of hydrogen bonding, such as ammonia electrooxidation and CO 2 hydrogenation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Infrastructure first principles for the Anthropocene

Abstract There appears to be a growing decoupling between the conditions that infrastructures were designed for and today’s rapidly changing environments. Infrastructures today are largely predicated on the technologies, goals, and governance structures from a century ago. While infrastructures continue to deliver untold value, there is growing evidence that these critical, basic, and lifeline systems appear ill-equipped to confront the volatility, uncertainty, accelerating conditions, and complexity that define them and their changing environments. Innovative and disruptive first principles are needed to guide infrastructures in the Anthropocene. Drawing from emerging infrastructure research and disciplines that appear better able to confront disruption and change, a novel set of first principles are identified: (1) Plan for complex conditions and surprise; (2) Recouple with agility and flexibility; (3) Govern for exploration and instability; (4) Build consensus as control decentralizes; (5) Restructure to engage with porous boundaries; and, (6) Cyberthreat planning is now mission critical. These principles should guide infrastructure planning recognizing the changing nature and increasingly obsolete boundaries that have defined engineered systems in the modern era.

Chester, Mikhail (ORCID:0000000293542102)↗
DOE OSTI2024

E min : A First-Principles Thermochemical Descriptor for Predicting Molecular Synthesizability

Predicting the synthesizability of a new molecule remains an unsolved challenge that chemists have long tackled with heuristic approaches. Here, in this study, we report a new method for predicting synthesizability using a simple yet accurate thermochemical descriptor. We introduce E min , the energy difference between a molecule and its lowest energy constitutional isomer, as a synthesizability predictor that is accurate, physically meaningful, and first-principles based. We apply E min to 134,000 molecules in the QM9 data set and find that E min is accurate when used alone and reduces incorrect predictions of "synthesizable" by up to 52% when used to augment commonly used prediction methods. Our work illustrates how first-principles thermochemistry and heuristic approximations for molecular stability are complementary, opening a new direction for synthesizability prediction methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

First-principles analysis of X-ray magnetic circular dichroism for transition metal complex oxides

X-ray magnetic circular dichroism (XMCD) is widely used for the characterization of magnetism of materials. However, information from XMCD related to the atomic, electronic, and magnetic structures is not fully utilized due to the lack of reliable theoretical tools for spectral analysis. In this work, the first-principles configuration interaction (CI) calculations for X-ray absorption spectra developed by the author were extended for the calculation of XMCD, where the Zeeman energy was taken into the Hamiltonian of the CI to mimic magnetic polarization in the solid state. This technique was applied to interpret the L{sub 2,3} XMCD from 3d transition metal complex oxides, such as NiFe{sub 2}O{sub 4} and FeTiO{sub 3}. The experimental XMCD spectra were quantitatively reproduced using this method. The oxidation states as well as the magnetic ordering between transition metal ions on crystallographically different sites in NiFe{sub 2}O{sub 4} can be unambiguously determined. A first-principles analysis of XMCD in FeTiO{sub 3} revealed the presence of Fe{sup 3+} and Ti{sup 3+} ions, which indicates that the charge transfer from Fe to Ti ions occurs. The origin of magnetic polarization of Ti ions in FeTiO{sub 3} was also discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2017

Atomic-scale structural and electronic properties of SrTiO 3 / GaAs interfaces: A combined STEM-EELS and first-principles study

The electronic properties of epitaxial oxide thin films grown on compound semiconductors are largely determined by the interfacial atomic structure, as well as the thermodynamic conditions during synthesis. Ferroelectric polarization and Fermi-level pinning in SrTiO 3 films have been attributed to the presence of oxygen vacancies at the oxide/semiconductor interface. Here, we present scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy analyses of GaAs films grown on SrTiO 3 combined with first-principles calculations to determine the atomic and electronic structures of the SrTiO 3 /GaAs interfaces. In this work, an atomically abrupt SrO/As interface is observed and the interfacial SrO layer is found to be O-deficient. First-principles density functional theory (DFT) calculations show SrO/Ga and Sr/As interfaces are favorable under O-rich and O-poor conditions, respectively. The SrO/Ga interface is reconstructed via the formation of Ga-Ga dimers while the Sr/As interface is abrupt and consistent with the experiment. DFT calculations further reveal that intrinsic two-dimensional electron gas (2DEG) forms in both SrO/Ga and Sr/As interfaces, and the Fermi level is pinned to the localized 2DEG states. Interfacial O vacancies can enhance the 2DEG density while it is possible for Ga/As vacancies to unpin the Fermi level from the 2DEG states.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

A first-principles based description of the Hf-Ni system supported by high-temperature synchrotron experiments

Hf-Ni is an important binary system for high temperature alloys and shape memory alloys which has been investigated several times in the literature but often using samples of Hf contaminated by Zr. The thermodynamics of this system are remodeled in this work based on first-principles calculations and additional experiments using Hf with relatively low Zr contamination (0.25 wt. %). Diffusion couples in the Ni-rich portion of the Hf-Ni system heat treated at 1173, 1273 and 1373 K are used to measure phase stability and Hf solubility in the fcc phase. The solubility observed in fcc Ni from Ni/Ni 50 Hf 50 (at.%) diffusion couples is larger than that observed in previous experiments. These results are the only source fit to during modeling of the fcc solubility to mitigate effects from Zr contamination. Data in the literature suggests that the high temperature crystal structure of the B33 NiHf phase is, in fact, the B2 structure. High temperature synchrotron measurements provide confirmation of this crystal structure. Modeling of the B2 phase was aided by first-principles calculations using special quasi-random structures (SQS). Finally, the present CALPHAD model will prove useful when designing shape memory alloys containing Hf and when modeling the Hf activity in Ni-base high temperature alloys.

36 MATERIALS SCIENCE↗