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At least 1,081 records · Page 60
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Electronic Structure of Metallophthalocyanines, MPc (M = Fe, Co, Ni, Cu, Zn, Mg) and Fluorinated MPc

In this work, we compute the electronic structure and optical excitation energies of metal-free and transition-metal phthalocyanines (H2Pc and MPc for M = Fe, Co, Ni, Cu, Zn, Mg) using density functional theory with optimally tuned range-separated hybrid functionals (OT-RSH). We show that the OT-RSH approach provides photoemission spectra in quantitative agreement with experiments as well as optical band gaps within 10% of their experimental values, capturing the interplay of localized d-states and delocalized pi-pi* states for these organometallic compounds. We examine the tunability of MPcs and H 2 Pc through fluorination, resulting in quasi-rigid shifts of the molecular orbital energies by up to 0.7 eV. Our comprehensive data set provides a new computational benchmark for gas-phase phthalocyanines, significantly improving upon other density-functional-theory-based approaches.

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

Massively Parallel Quantum Chemistry: A high-performance research platform for electronic structure

The Massively Parallel Quantum Chemistry (MPQC) program is a 30-year-old project that enables facile development of electronic structure methods for molecules for efficient deployment to massively parallel computing architectures. Here, we describe the historical evolution of MPQC’s design into its latest (fourth) version, the capabilities and modular architecture of today’s MPQC, and how MPQC facilitates rapid composition of new methods as well as its state-of-the-art performance on a variety of commodity and high-end distributed-memory computer platforms.

Peng, Chong↗
NASA NTRS1995

Electronic structure and the van Hove singularity scenario in high-T(sub c)H(g)Ba2CuO(4+delta) superconductors

The electronic structure and the hole concentrations in the high Tc superconductor HgBa2CuO(4+delta) (delta = O, 1) has been investigated by employing a first principles full potential self-consistent LMTO method with the local density functional theory. The scalar relativistic effects have been considered. The hole concentrations of the Cu-d and O-p(x,y) orbitals are seen to be larger for the HgBaCuO5 system than those of the HgBaCuO4 solid. However, the van Hove singularity (vHs) induced Cu-d and O-p peak which is seen to lie comparatively away and above the Fermi level in the delta = 1 system shifts towards the Fermi level in the delta = 0 system. Thus, the superconducting behavior appears to originate from the occurrence of the vHs peak at the Fermi level. The Fermi surface nesting area in the delta = 0 compound is seen to be larger than in the delta = 1 compound. The calculation reveals that the increase in pressure on the crystal enhances the hole concentrations but without showing any optimum value, On the other hand, the vHs peak approaches to-wards the Fermi level with pressure and crosses the Fermi surface near V/Vo approximately equals 0.625 (V and Vo are the crystal volumes at high and normal pressures, respectively). Our calculated value of the bulk modulus equal to 0.626 Mbar predicts the occurrence of this crossover at about 24 GPa which is in complete agreement with the experimental value. At this pressure the compound has maximum nesting area and self-doped behavior.

Agrawal, Bal K.↗
DOE OSTI2019

First principle study of structural, electronic, optical, and transport properties of ternary compounds NaGaX{sub 2} (X = S, Se, and Te) in tetragonal chalcopyrite phase

Eemploying the all electron full potential linearized augmented plane wave plus local orbital (FP-LAPW + lo) method based on density functional theory (DFT) structural, electronic, optical, and transport properties of compounds NaGaX{sub 2} (X = S, Se, and Te) in tetragonal phase have been investigated at ground state. The exchange-correlation effects have been included using the Wu Cohen (WC) generalized gradient approximation (GGA) and modified Becke–Johnson (mBJ) exchange potentials. Enthalpy of formation values ensure that crystal structures are stable in tetragonal chalcopyrite phase. Total and partial density of states, and band structures have been plotted to calculate electronic properties which exhibits direct band gap for all compounds. The electronic band gap of NaGaS{sub 2} (2.1 eV) is found to be higher than the electronic band gaps of NaGaSe{sub 2} (1.7 eV) and NaGaTe{sub 2} (1.2 eV) compounds. Using real and imaginary parts of the dielectric function, optical properties such as refractive index (n), extinction coefficient (k), reflectivity (R), absorption coefficient (α), and energy loss spectrum (L) were determined. Transport properties like Seebeck coefficient, thermal and electrical conductivities, figure of merit, and power factors have also been reported by combining the results from DFT and Boltzmann transport theory. The high absorption peaks in visible and ultraviolet regions of the energy spectrum and direct band gaps of these compounds ensure that three compounds are promising materials for photovoltaic applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Effect of atomic-scale defects and dopants on phosphorene electronic structure and quantum transport properties

By means of a multi-scale first-principles approach, a description of the local electronic structure of 2D and narrow phosphorene sheets with various types of modifications is presented. Firtly, a rational argument based on the geometry of the pristine and modified P network, and supported by the Wannier functions formalism is introduced to describe a hybridization model of the P atomic orbitals. Ab initio calculations show that non-isoelectronic foreign atoms form quasi-bound states at varying energy levels and create different polarization states depending on the number of valence electrons between P and the doping atom. The quantum transport properties of modified phosphorene ribbons are further described with great accuracy. The distortions on the electronic bands induced by the external species lead to strong backscattering effects on the propagating charge carriers. Depending on the energy of the charge carrier and the type of doping, the conduction may range from the diffusive to the localized regime. Interstitial defects at vacant sites lead to homogeneous transport fingerprints across different types of doping atoms. We suggest that the relatively low values of charge mobility reported in experimental measurements may have its origin in the presence of defects.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Probing the electronic structure and Au—C chemical bonding in AuC{sub n}{sup −} and AuC{sub n}H{sup −} (n = 2, 4, and 6) using high-resolution photoelectron spectroscopy

We report a joint photoelectron spectroscopy and theoretical study on AuC{sub 4}{sup −}, AuC{sub 6}{sup −}, and AuC{sub n}H{sup −} (n = 2, 4, and 6) using high-resolution photoelectron imaging and ab initio calculations. The ground state of AuC{sub 2}H{sup −}, AuC{sub 4}H{sup −}, and AuC{sub 6}H{sup −} is found to be linear, while that of AuC{sub 4}{sup −} and AuC{sub 6}{sup −} is bent. All the species are found to be linear in their neutral ground states. The electron affinities (EAs) are measured to be 3.366(1) and 3.593(1) eV for AuC{sub 4} and AuC{sub 6}, respectively. Both bending and stretching frequencies are resolved in the spectra of AuC{sub 4}{sup −} and AuC{sub 6}{sup −}. High-resolution data of AuC{sub n}H{sup −} reveal major vibrational progressions in the Au—C stretching and bending modes. AuC{sub 2}H{sup −} has a ground state stretching frequency of 445(10) cm{sup −1} and a bending frequency of 260(10) cm{sup −1}; AuC{sub 4}H{sup −} has a ground state stretching frequency of 340(10) cm{sup −1}; AuC{sub 6}H{sup −} has a ground state stretching frequency of 260(10) cm{sup −1} and a bending frequency of 55(10) cm{sup −1}. The EAs are measured to be 1.475(1), 1.778(1), and 1.962(1) eV for AuC{sub 2}H, AuC{sub 4}H, and AuC{sub 6}H, respectively. The strength of the Au—C bond decreases as the number of carbon atoms increases. The current study provides a wealth of electronic structure information about AuC{sub 4}{sup −}, AuC{sub 6}{sup −}, and AuC{sub n}H{sup −} (n = 2, 4, and 6) and their corresponding neutrals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Electronic structure of Al- and Ga-doped ZnO films studied by hard X-ray photoelectron spectroscopy

Al- and Ga-doped sputtered ZnO films (AZO, GZO) are semiconducting and metallic, respectively, despite the same electronic valence structure of the dopants. Using hard X-ray photoelectron spectroscopy we observe that both dopants induce a band in the electronic structure near the Fermi level, accompanied by a narrowing of the Zn 3d/O 2p gap in the valence band and, in the case of GZO, a substantial shift in the Zn 3d. Ga occupies substitutional sites, whereas Al dopants are in both substitutional and interstitial sites. The latter could induce O and Zn defects, which act as acceptors explaining the semiconducting character of AZO and the lack of variation in the optical gap. By contrast, mainly substitutional doping is consistent with the metallic-like behavior of GZO.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Synchrotron radiation photoemission study of interfacial electronic structure of HfO{sub 2} on In{sub 0.53}Ga{sub 0.47}As(001)-4 × 2 from atomic layer deposition

The growth of a passivating layer on a In{sub 0.53}Ga{sub 0.47}As(001)-4 × 2 surface by atomic-layer deposition of tetrakis[ethylmethylamino]Hafnium (TEMAHf)) followed by the water pulse was investigated by synchrotron radiation photoemission. The Hf atoms maintain four-fold coordination, both after the initial TEMAHf deposition and the subsequent water pulse. The Hf atoms initially bond to the As dangling bonds of the surface As atom located on the edges of the raised ridges. One EMA ligand is removed in this process. Subsequent water exposure substitutes OH ligand for one or more remaining EMA ligands. These in turn react with TEMAHf to form Hf-O-Hf bonds allowing the hafnium oxides to grow. The surface In atoms on the terrace of the raised ridges were partially removed, but none bonded of the precursor atoms. Correlations between the interfacial electronic structure and the electric performance are discussed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Electronic Structure Progression across the ACu 2 Q 2 (MQ 2 ) n Semiconductor Series

Moving beyond the engineering of known materials and elemental substitution within common structure types is critical for designing unique properties. Here, we present a new homologous series, ACu 2 Q 2 (MQ 2 ) n (A = Sr, Ba, 2Na; MQ 2 = ZrS2, HfSe 2 ), establishing 11 new members. In β-BaCu 2 Q 2 and Na 2 Cu 2 Se 2 (n = 0), the [Cu 2 Q 2 ] 2– motifs extend in two dimensions, whereas those in α-BaCu 2 Q 2 extend in three dimensions. Hence, there are two structural evolutions within the ACu 2 Q 2 (MQ 2 )n family driven by the polymorphism of the host structures. MQ 2 (n → ∞) displays 2D layers of edge-sharing [MQ 6 ] 8– octahedra that are 1-octahedron-thick and connected via van der Waals bonding. Each insertion of MQ 2 into ACu 2 Q 2 incorporates [MQ 6 ] 8– octahedra extending infinitely in one direction, confined to being 1-octahedron-thick in the second direction, with n controlling the number of [MQ 6 ] 8– octahedra in the third direction. Therefore, increasing n predictively expands the [Cu 2 MnQ 2n+2 ] 2– network in the direction controlled by n and relative to the A + /A 2+ ions. We demonstrate that for a given set of elements, one can enforce a “Host(Insertion)n” formula to systematically evolve both crystal and electronic structures from the host (n = 0) to the insertion (n → ∞) materials through intermediate values of n. Specifically, the energetic misalignment of the electronic band extrema of the parents predictively determines the band extrema and the resulting band gaps of all intermediate n members.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Tunable electronic structure in gallium chalcogenide van der Waals compounds

Transition-metal monochalcogenides comprise a class of two-dimensional materials with electronic band gaps that are highly sensitive to material thickness and chemical composition. Here, we explore the tunability of the electronic excitation spectrum in GaSe by using angle-resolved photoemission spectroscopy. The electronic structure of the material is modified by in situ potassium deposition as well as by forming GaS x Se 1- x alloy compounds. We find that potassium-dosed samples exhibit a substantial change of the dispersion around the valence-band maximum (VBM). The observed band dispersion resembles that of a single tetralayer and is consistent with a transition from the direct-gap character of the bulk to the indirect-gap character expected for monolayer GaSe. Upon alloying with sulfur, we observe a phase transition from AB to AA' stacking. Alloying also results in a rigid energy shift of the VBM towards higher binding energies, which correlates with a blueshift in the luminescence. The increase of the band gap upon sulfur alloying does not appear to change the dispersion or character of the VBM appreciably, implying that it is possible to engineer the gap of these materials while maintaining their salient electronic properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Critical Assessment of Electronic Structure Descriptors for Predicting Perovskite Catalytic Properties

The discovery and design of materials which can efficiently catalyze the oxygen reduction and evolution reactions at reduced temperatures is important for facilitating the widespread adoption of fuel cell and electrolyzer technologies. Numerous studies have produced correlations between catalytic properties, such as oxygen surface exchange or electrode area specific resistance (ASR), and properties of the catalyst material. However, correlations have historically been limited in scope (e.g., using only a few materials or at a single temperature) and it has been difficult to provide detailed assessments of their robustness. Here, in this study, we assess the ability of the O p-band center electronic structure descriptor, obtained from density functional theory (DFT) calculations, to correlate with oxygen surface exchange rates, diffusivities, and area specific resistances for a large database of perovskite oxide catalytic properties. By data mining the literature, we obtain 747 catalytic property value data points spanning 299 unique perovskite compositions from 313 studies. We assess linear correlations of each property with the O p-band center and find generally modest correlations that are qualitatively useful (prediction mean absolute errors of about 0.5 log units are typical), where the correlations are improved at higher temperatures (e.g., 800 °C vs. 500 °C) and significantly improve when considering fits to the subset of materials which have multiple independent measurements. These findings suggest that the spread of property data is significantly influenced by experimental uncertainty, and subsequent measurements of additional materials will likely improve the O p-band center correlations.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2015

Electrical/thermal transport and electronic structure of the binary cobalt pnictides CoPn{sub 2} (Pn = As and Sb)

We demonstrate the electrical and thermal transport properties of polycrystalline CoPn{sub 2} (Pn = As and Sb) between 300 and 900 K. CoAs{sub 2} shows semiconducting electrical transport up to 900 K, while CoSb{sub 2} exhibits degenerate conduction. Sign inversion of the Seebeck coefficient is observed at ∼310 and ∼400 K for CoAs{sub 2} and CoSb{sub 2}, respectively. Thermal conductivity at 300 K is 11.7 Wm{sup −1}K{sup −1} for CoAs{sub 2} and 9.4 Wm{sup −1}K{sup −1} for CoSb{sub 2}. The thermoelectric power factor of CoAs{sub 2} is ∼10 μWcm{sup −1}K{sup −2}, although the dimensionless figure of merit is limited to ∼0.1 due to relatively high thermal conductivity. Using electronic structure calculations, the band gap value is calculated to be 0.55 eV for CoAs{sub 2} and 0.26 eV for CoSb{sub 2}.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Electronic structure of fully epitaxial Co{sub 2}TiSn thin films

We report on the properties of thin films of the full Heusler compound Co{sub 2}TiSn prepared by dc magnetron co-sputtering. Fully epitaxial, stoichiometric films were obtained by deposition on MgO (001) substrates at substrate temperatures above 600 C. The films are well ordered in the L2{sub 1} structure, and the Curie temperature slightly exceeds the bulk value. They show a significant, isotropic magnetoresistance and the resistivity becomes strongly anomalous in the paramagnetic state. The films are weakly ferrimagnetic, with nearly 1 {mu}{sub B} on the Co atoms, and a small antiparallel Ti moment, in agreement with theoretical expectations. From comparison of x-ray absorption spectra on the Co L{sub 3,2} edges, including circular and linear magnetic dichroism, with ab initio calculations of the x-ray absorption and circular dichroism spectra we infer that the electronic structure of Co{sub 2}TiSn has essentially nonlocalized character. Spectral features that have not been explained in detail before are explained here in terms of the final-state band structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Methanol synthesis on ZnO(0001{sup ¯}). IV. Reaction mechanisms and electronic structure

Methanol synthesis from CO and H{sub 2} over ZnO, which requires high temperatures and high pressures giving rise to a complex interplay of physical and chemical processes over this heterogeneous catalyst surface, is investigated using ab initio simulations. The redox properties of the surrounding gas phase are known to directly impact on the catalyst properties and thus, set the overall catalytic reactivity of this easily reducible oxide material. In Paper III of our series [J. Kiss, J. Frenzel, N. N. Nair, B. Meyer, and D. Marx, J. Chem. Phys. 134, 064710 (2011)] we have qualitatively shown that for the partially hydroxylated and defective ZnO(0001{sup ¯}) surface there exists an intricate network of surface chemical reactions. In the present study, we employ advanced molecular dynamics techniques to resolve in detail this reaction network in terms of elementary steps on the defective surface, which is in stepwise equilibrium with the gas phase. The two individual reduction steps were investigated by ab initio metadynamics sampling of free energy landscapes in three-dimensional reaction subspaces. By also sampling adsorption and desorption processes and thus molecular species that are in the gas phase but close to the surface, our approach successfully generated several alternative pathways of methanol synthesis. The obtained results suggest an Eley-Rideal mechanism for both reduction steps, thus involving “near-surface” molecules from the gas phase, to give methanol preferentially over a strongly reduced catalyst surface, while important side reactions are of Langmuir-Hinshelwood type. Catalyst re-reduction by H{sub 2} stemming from the gas phase is a crucial process after each reduction step in order to maintain the catalyst's activity toward methanol formation and to close the catalytic cycle in some reaction channels. Furthermore, the role of oxygen vacancies, side reactions, and spectator species is investigated and mechanistic details are discussed based on extensive electronic structure analysis.

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

Theory of the electronic structure of dilute bismide and bismide-nitride alloys of GaAs: Tight-binding and k.p models

The addition of dilute concentrations of bismuth (Bi) into GaAs to form GaBi{sub x}As{sub 1−x} alloys results in a large reduction of the band gap energy (E{sub g}) accompanied by a significant increase of the spin-orbit-splitting energy (Δ{sub SO}), leading to an E{sub g} < Δ{sub SO} regime for x ∼ 10% which is technologically relevant for the design of highly efficient photonic devices. The quaternary alloy GaBi{sub x}N{sub y}As{sub 1−x−y} offers further flexibility for band gap tuning, because both nitrogen and bismuth can independently induce band gap reduction. This work reports sp{sup 3}s* tight binding and 14-band k⋅p models for the study of the electronic structure of GaBi{sub x}As{sub 1−x} and GaBi{sub x}N{sub y}As{sub 1−x−y} alloys. Our results are in good agreement with the available experimental data.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Advanced Electronic Structure Calculations For Nanoelectronics Using Finite Element Bases and Effective Mass Theory.

This paper describes our work over the past few years to use tools from quantum chemistry to describe electronic structure of nanoelectronic devices. These devices, dubbed "artificial atoms", comprise a few electrons, con ned by semiconductor heterostructures, impurities, and patterned electrodes, and are of intense interest due to potential applications in quantum information processing, quantum sensing, and extreme-scale classical logic. We detail two approaches we have employed: nite-element and Gaussian basis sets, exploring the interesting complications that arise when techniques that were intended to apply to atomic systems are instead used for artificial, solid-state devices.

Gamble, John King↗
DOE OSTI2019

Electronic structure as a guide in screening for potential thermoelectrics: Demonstration for half-Heusler compounds

In this study, we adopt a high-throughput search strategy that begins with electronic structure features to screen a set of half-Heusler compounds for thermoelectric performance. This is motivated by the contradictory electrical transport requirements, specifically high electrical conductivity σ and high thermopower S for obtaining high figure of merit ZT. We use an electronic fitness function that measures the extent to which a specific band structure decouples σ and S for this purpose. We then perform detailed, more costly, calculations of thermal conductivity and electrical properties for those compounds that have a high electronic fitness. This provides an efficient method for identifying promising compounds from a set of candidates. Lastly, we apply this to a set of 75 previously studied half-Heusler compounds. The approach identifies several compounds as having potential as thermoelectric materials. Importantly, these include not only some previously identified candidates, but also some other compounds that had not been identified previously using other screening methods.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Multiscale real-space quantum-mechanical tight-binding calculations of electronic structure in crystals with defects using perfectly matched layers

Graphical abstract: - Abstract: We consider the scattering of incident plane-wave electrons from a defect in a crystal modeled by the time-harmonic Schrödinger equation. While the defect potential is localized, the far-field potential is periodic, unlike standard free-space scattering problems. Previous work on the Schrödinger equation has been almost entirely in free-space conditions; a few works on crystals have been in one-dimension. We construct absorbing boundary conditions for this problem using perfectly matched layers in a tight-binding formulation. Using the example of a point defect in graphene, we examine the efficiency and convergence of the proposed absorbing boundary condition.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗