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At least 1,297 records · Page 72
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Electronic structure of the frustrated diamond lattice magnet NiRh 2 O 4

We report the A -site spinel NiRh 2 O 4 is the only known realization of a spin-1 diamond lattice magnet and is predicted to host unconventional magnetic phenomena driven by frustrated nearest and next-nearest neighbor exchange as well as orbital degeneracy. Previous works found no sign of magnetic order but found a gapped dispersive magnetic excitation indicating a possible valence bond magnetic ground state. However, the presence of many competing low energy degrees of freedom and limited empirical microscopic constraints complicates further analysis. Here we carry out resonant inelastic x-ray scattering (RIXS), x-ray absorption spectroscopy (XAS), and inelastic neutron scattering (INS) to characterize the local electronic structure and lattice dynamics of NiRh 2 O 4 . The RIXS data can be partly described by a single-ion model for tetrahedrally coordinated Ni 2+ and indicates a tetragonal distortion Δt 2 = 70 meV that splits the t 2 orbitals into a high energy orbital singlet and lower energy orbital doublet. We identify features of the RIXS spectra that are consistent with a Rh-Ni two-site excitation indicating strong metal-metal hybridization mediated by oxygen in NiRh 2 O 4 . We also identify signatures of electron-phonon coupling through the appearance of phonon sidebands that dress crystal field excitations. These results establish the key energy scales relevant to the magnetism in NiRh 2 O 4 and further demonstrate that covalency and lattice dynamics play essential roles in controlling the magnetic ground states of A -site spinels.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Projected Commutator DIIS Method for Accelerating Hybrid Functional Electronic Structure Calculations

The commutator direct inversion of the iterative subspace (commutator DIIS or C-DIIS) method developed by Pulay is an efficient and the most widely used scheme in quantum chemistry to accelerate the convergence of self-consistent field (SCF) iterations in Hartree–Fock theory and Kohn–Sham density functional theory. The C-DIIS method requires the explicit storage of the density matrix, the Fock matrix, and the commutator matrix. Hence, the method can only be used for systems with a relatively small basis set, such as the Gaussian basis set. We develop a new method that enables the C-DIIS method to be efficiently employed in electronic structure calculations with a large basis set such as planewaves for the first time. The key ingredient is the projection of both the density matrix and the commutator matrix to an auxiliary matrix called the gauge-fixing matrix. The resulting projected commutator-DIIS method (PC-DIIS) only operates on matrices of the same dimension as that consists of Kohn–Sham orbitals. The cost of the method is comparable to that of standard charge mixing schemes used in large basis set calculations. The PC-DIIS method is gauge-invariant, which guarantees that its performance is invariant with respect to any unitary transformation of the Kohn–Sham orbitals. We demonstrate that the PC-DIIS method can be viewed as an extension of an iterative eigensolver for nonlinear problems. We use the PC-DIIS method for accelerating Kohn–Sham density functional theory calculations with hybrid exchange–correlation functionals, and demonstrate its superior performance compared to the commonly used nested two-level SCF iteration procedure. Furthermore, we demonstrate that in the context of ab initio molecular dynamics (MD) simulation with hybrid functionals one can extrapolate the gauge-fixing matrix to achieve the goal of extrapolating the entire density matrix implicitly along the MD trajectory. Here, numerical results indicate that the new method significantly reduces the number of SCF iterations per MD step, compared to the commonly used strategy of extrapolating the electron density.

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

Temperature-dependent electronic structure in a higher-order topological insulator candidate EuIn 2 As 2

Higher-order topological insulators (HOTIs) have enticed enormous research interests owing to their novelty in supporting gapless states along the hinges of a crystal. Despite several theoretical predictions, enough experimental confirmation of the HOTI state in crystalline solids is still lacking. Here, it is shown that interplay between topology and magnetism can give rise to various magnetic topological states, including HOTI and axion insulator states. Here, using high-resolution angle-resolved photoemission spectroscopy combined with the first-principles calculations, we report a systematic study of the electronic structure and its evolution across the magnetic phase transition in EuIn 2 As 2 which possesses an antiferromagnetic ground state below 16 K. Antiferromagnetic EuIn 2 As 2 has been predicted to host both the axion insulator and the HOTI states.We directly observe the linearly dispersing holelike bands crossing the Fermi level and the change in their dispersion across the magnetic phase transition. Our paper points to EuIn 2 As 2 as being a promising material for the exploration of interplay between topology and magnetism.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

Electronic structure and absorption spectrum of biexciton obtained by using exciton basis

We approach the biexciton Schrödinger equation not through the free-carrier basis as usually done, but through the free-exciton basis, exciton–exciton interactions being treated according to the recently developed composite boson many-body formalism which allows an exact handling of carrier exchange between excitons, as induced by the Pauli exclusion principle. We numerically solve the resulting biexciton Schrödinger equation with the exciton levels restricted to the ground state and we derive the biexciton ground state as well as the bound and unbound excited states as a function of hole-to-electron mass ratio. The biexciton ground-state energy we find, agrees reasonably well with variational results. Next, we use the obtained biexciton wave functions to calculate optical absorption in the presence of a dilute exciton gas in quantum well. We find an asymmetric peak with a characteristic low-energy tail, identified with the biexciton ground state, and a set of Lorentzian-like peaks associated with biexciton unbound states, i.e., exciton–exciton scattering states. Last, we propose a pump–probe experiment to probe the momentum distribution of the exciton condensate. -- Highlights: •New composite boson many-body theory is used to derive exactly the biexciton Schrödinger equation using the exciton basis. •We solved the 2D and 3D biexciton ground- and excited-state binding energies for various electron-to-hole mass ratios. •The absorption spectrum shows an asymmetric low-energy peak identified with the biexciton ground state. •High-energy Lorentzian-like peaks in the absorption spectrum are associated with the exciton–exciton scattering states. •The exciton gas momentum distribution can be determined by the absorption spectrum via the biexciton wave functions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Effect of 3d/4p Mixing on 1s2p Resonant Inelastic X-ray Scattering: Electronic Structure of Oxo-Bridged Iron Dimers

1s2p resonant inelastic X-ray scattering (1s2p RIXS) has proven successful in the determination of the differential orbital covalency (DOC, the amount of metal vs ligand character in each d molecular orbital) of highly covalent centrosymmetric iron environments including heme models and enzymes. However, many reactive intermediates have noncentrosymmetric environments, e.g., the presence of strong metal-oxo bonds, which results in the mixing of metal 4p character into the 3d orbitals. This leads to significant intensity enhancement in the metal K-pre-edge and as shown here, the associated 1s2p RIXS features, which impact their insight into electronic structure. Binuclear oxo bridged high spin Fe(III) complexes are used to determine the effects of 4p mixing on 1s2p RIXS spectra. In addition to developing the analysis of 4p mixing on K-edge XAS and 1s2p RIXS data, this study explains the selective nature of the 4p mixing that also enhances the analysis of L-edge XAS intensity in terms of DOC. These 1s2p RIXS biferric model studies enable new structural insight from related data on peroxo bridged biferric enzyme intermediates. The dimeric nature of the oxo bridged Fe(III) complexes further results in ligand-to-ligand interactions between the Fe(III) sites and angle dependent features just above the pre-edge that reflect the superexchange pathway of the oxo bridge. Lastly, we present a methodology that enables DOC to be obtained when L-edge XAS is inaccessible and only 1s2p RIXS experiments can be performed as in many metalloenzyme intermediates in solution.

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

Electronic structure of epitaxial half-Heusler Co 1-x Ni x TiSb across the semiconductor to metal transition

In this paper, we report on the growth, electronic, and surface properties of the electron-doped half-Heusler series Co 1-x Ni x TiSb (001) grown by molecular beam epitaxy. High-quality epitaxial growth of thin films is achieved on InP (001) substrates using an InAlAs buffer layer for all nickel concentrations. The semiconductor to metal transition as a function of substitutional alloying was examined using electrical transport, Seebeck measurements, and angle-resolved photoemission spectroscopy (ARPES). Temperature-dependent electrical transport measurements of films with composition x ≤ 0.1 exhibit thermally activated behavior while x > 0.1 exhibit metallic behavior. Smooth, highly ordered film surfaces can be achieved following ex-situ transfer of the films and subsequent desorption of a sacrificial, protective antimony capping layer. Using this transfer technique, ARPES experiments were performed to investigate the effects of nickel alloying on the electronic band structure. Finally, an electron pocket is observed below the Fermi level at the bulk X point for compositions x > 0.1, in accordance with the crossover from semiconducting to metallic behavior observed in the transport measurements.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Electronic Structure and Performance Bottlenecks of CuFeO 2 Photocathodes

The path to realizing low-cost, stable, and earth-abundant photoelectrodes can be enabled through a detailed understanding of the optoelectronic properties of these materials by combining theory and experimental techniques. Of the limited set of oxide photocathode materials currently available, CuFeO 2 has emerged as a promising candidate warranting detailed attention. Here, highly compact thin films of rhombohedral (3R) CuFeO 2 were prepared via reactive co-sputtering. Despite its 1.43 eV indirect band gap, a cathodic photocurrent of 0.85 mA/cm 2 was obtained at 0.4 V versus reversible hydrogen electrode in the presence of a sacrificial electron acceptor. This unexpected performance was related to inefficient bulk charge separation because of the ultrafast (<1 ps) self-trapping of photogenerated free carriers. The electronic structure of 3R-CuFeO 2 was elucidated through a combination of optical and X-ray spectroscopic techniques and further complemented by first-principles computational methods including a many-body approach for computing the O K-edge X-ray absorption spectrum. Through resonant inelastic X-ray scattering spectroscopy, the visible absorption edges of CuFeO 2 were found to correspond to Cu → Fe metal-to-metal charge transfer, which exhibits a high propensity toward self-trapping. Findings of the present work enable us to understand the performance bottlenecks of CuFeO 2 photocathodes and suggest feasible strategies for improving material limitations.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Electronic structure of monolayer 1T'-MoTe 2 grown by molecular beam epitaxy

Monolayer transition metal dichalcogenides (TMDCs) in the 1T' structural phase have drawn a great deal of attention due to the prediction of quantum spin Hall insulator states. The band inversion and the concomitant changes in the band topology induced by the structural distortion from 1T to 1T' phases are well established. However, the bandgap opening due to the strong spin-orbit coupling (SOC) is only verified for 1T'-WTe 2 recently and still debated for other TMDCs. Here we report a successful growth of high-quality monolayer 1T'-MoTe 2 on a bilayer graphene substrate through molecular beam epitaxy. Using in situ angle-resolved photoemission spectroscopy (ARPES), we have investigated the low-energy electronic structure and Fermi surface topology. The SOC-induced breaking of the band degeneracy points between the valence and conduction bands is clearly observed by ARPES. However, the strength of SOC is found to be insufficient to open a bandgap, which makes monolayer 1T'-MoTe 2 on bilayer graphene a semimetal.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Dehydration of the Uranyl Peroxide Studtite, [UO 2 (η 2 -O 2 )(H 2 O) 2 ]·2H 2 O, Affords a Drastic Change in the Electronic Structure: A Combined X-ray Spectroscopic and Theoretical Analysis

The dehydration of studtite, [UO 2 (2-O 2 )(H 2 O)2]·2H 2 O, to metastudtite, [UO 2 (2-O 2 )(H 2 O) 2 ], uranyl peroxide minerals that are major oxidative alteration phases of UO2 under conditions of geological storage, has been studied using X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy. XPS of the U 4f region shows small but significant differences between studtite and metastudtite, with the 4f binding energy of studtite the highest reported for a uranyl mineral studied by this technique. Further information on the changes in the electronic structure was elucidated using U M4-edge High Energy Resolution XANES (HR-XANES) spectroscopy, which directly probes f-orbital states. The transition from the 3d to the 5f* orbital is sensitive to variations of the U=Oaxial bond length and to changes in the bond covalency. We report evidences that the covalence in the uranyl fragment decreases upon dehydration. Photoluminescence spectroscopy at near liquid helium temperatures reveals significant spectral differences between the two materials, correlating with the X-ray spectroscopy results. A theoretical investigation has been conducted on the structures of both studtite and metastudtite and benchmarked to the HR-XANES spectra. These illustrate the sensitivity of the 3d to the 5f * transition towards U=Oaxial bond variation.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2014

Electronic Structure, Dielectric Response and Surface Charge Distribution of RGD (1FUV) Peptide

Long and short range molecular interactions govern molecular recognition and self-assembly of biological macromolecules. Microscopic parameters in the theories of these molecular interactions are either phenomenological or need to be calculated within a microscopic theory. We report a unified methodology for the ab initio quantum mechanical (QM) calculation that yields all the microscopic parameters, namely the partial charges as well as the frequency-dependent dielectric response function, that can then be taken as input for macroscopic theories of electrostatic, polar, and van der Waals-London dispersion intermolecular forces. We apply this methodology to obtain the electronic structure of the cyclic tripeptide RGD-4C (1FUV). This ab initio unified methodology yields the relevant parameters entering the long range interactions of biological macromolecules, providing accurate data for the partial charge distribution and the frequency-dependent dielectric response function of this peptide. These microscopic parameters determine the range and strength of the intricate intermolecular interactions between potential docking sites of the RGD-4C ligand and its integrin receptor.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Assessment of DFT methods for the prediction of detachment energies and electronic structures of complex and multiply charged anions

Here, in this work, we assess the ability of different density functional theory methods to reproduce the vertical/adiabatic detachment energies (VDEs/ADEs) of a series of 40 anions, including monoanion versus multiply charged anions (MCAs) and covalent versus noncovalent interaction. The statistical analysis of errors is firstly performed by comparing the theoretical values with the experimental benchmark data obtained from the negative ion photoelectron spectroscopy (NIPES). The proposed optimally tuned range-separated (OTRS) functionals are proved to not only well reproduce the experimental VDEs/ADEs, but also simulate experimental NIPES. The result implies a more serious issue of delocalization error for MCAs and a balanced description of electron-rich/- deficient region of anions is necessary. The radius of the spherically symmetric average electron localization function (ELF) region is demonstrated as a useful descriptor for the characterization of electronic structure of anionic systems and a quasilinear fitting model is proposed to efficiently obtain their OTRS parameters.

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

Electronic structure and rovibrational properties of ZnOH in the X{sup ~2}A{sup ′} electronic state: A computational molecular spectroscopy study

The three-dimensional ground-state potential energy surface of ZnOH has been calculated ab initio at the MR-SDCI+Q-DK3/[QZP ANO-RCC (Zn, O, H)] level of theory and used as basis for a study of the rovibrational properties carried out by means of the program MORBID (Morse Oscillator Rigid Bender Internal Dynamics). The electronic ground state is {sup 2}A′ (correlating with {sup 2}Σ{sup +} at the linear configuration). The equilibrium structure has r{sub e}(Zn–O) = 1.8028 Å, r{sub e}(O–H) = 0.9606 Å, and ∠{sub e}(Zn–O–H) = 114.9°. The Zn–O bond is essentially ionic, with appreciable covalency. The bonding character is compared with those of FeOH (quasi-linear) and CsOH (linear). The rovibrationally averaged structural parameters, determined as expectation values over MORBID wavefunctions, are 〈r(Zn–O)〉{sub 0} = 1.8078 Å, 〈r(O–H)〉{sub 0} = 0.9778 Å, and 〈∠(Zn–O–H)〉{sub 0} = 117°. The Yamada-Winnewisser quasi-linearity parameter is found to be γ{sub 0} = 0.84, which is close to 1.0 as expected for a bent molecule. Since no experimental rovibrational spectrum has been reported thus far, this spectrum has been simulated from the ab initio potential energy and dipole moment surfaces. The amphoteric character of ZnOH is also discussed.

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

Surface and electronic structure at atomic length scales of the nonsymmorphic antiferromagnet Eu 5 In 2 Sb 6

We performed scanning tunneling microscopy and spectroscopy (STM/STS) measurements to investigate the Zintl phase Eu 5 ⁢In 2 ⁢Sb 6 , a nonsymmorphic antiferromagnet. The theoretical prediction of a nontrivial Fermi surface topology stabilized by the nonsymmorphic symmetry motivated our research. On the cleaved (010) plane, we obtained striped patterns that can be correlated to the stacking of the [In 2 ⁢Sb 6 ] 10- double chains along the crystallographic c axis. The attempted cleavage along the a axis revealed a more complex pattern. We combined the STS measurement on nonreconstructed (010) and (081) surfaces with DFT calculations to further elucidate the electronic structure of Eu 5 ⁢In 2 ⁢Sb 6 . From our investigations so far, direct experimental evidence of the predicted topological surface states remains elusive.

36 MATERIALS SCIENCE↗
DOE OSTI2016

First-principles study of structural & electronic properties of pyramidal silicon nanowire

We have investigated the stable structural and electronic properties of Silicon (Si) nanowires having different cross-sections with 5-7 Si atoms per unit cell. These properties of the studied Si nanowires were significantly changed from those of diamond bulk Si structure. The binding energy increases as increasing atoms number per unit cell in different SiNWs structures. All the nanowires structures are behave like metallic rather than semiconductor in bulk systems. In general, the number of conduction channels increases when the nanowire becomes thicker. The density of charge revealed delocalized metallic bonding for all studied Si nanowires.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Unexpected Hydricity of a Bis-Carbene Iridium Complex Provides Insight into Electronic Structure Impacts on Hydride Donor Ability

The hydricity (ΔG° H– ), or hydride donor ability, of a transition metal complex is a thermodynamic parameter which can aid in the design and interpretation of various catalytic reactions that involve hydride transfer as a key step. In an attempt to generate a strong hydride donor, the bis-carbene ligand 3,3′-methylenebis(1-methyl-imidazol-2-ylidene) (“bis-mim”) was installed in an iridium hydride complex, [Cp*Ir(bis-mim)H] + . Experimental and computational studies show that [Cp*Ir(bis-mim)H] + is actually a relatively weak hydride donor, however. To understand why the complex is an unexpectedly weak hydride donor, experimental and computational studies probing the steric and electronic effects on hydricity were conducted. Steric factors had a minimal impact on thermodynamic hydricity but dampened kinetic hydricity. In conclusion, the poor thermodynamic hydride donor ability can be attributed to an electronic structure that results in relatively long Cp*−Ir bonds, an unusually high Ir–H BDFE and pK a values that have an outsized influence on thermochemical cycles for hydricity.

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

Electronic structure of an anticancer drug DC81 and its interaction with DNA base pairs

The drug, 8-Hydroxy-7-methoxy-pyrrolo-[2,1-c][1,4] benzodiazepine-5-one, commonly christened as DC81 belongs to the pyrrolo-[2,1-c][1,4]benzodiazepine (PBDs) family. It is a member of the group of naturally occurring antitumour antibiotics produced by various Streptomyces species. The antitumour activity of DC81 is attributed to its sequence specific interaction with G-C rich DNA region in particular, for Pu-G-Pu motifs. In the present paper, physico-chemical properties DC81 have been carried out using an ab-initio method, HF/6-31G(d,p) with GAMESS program. MEP, HOMO and LUMO surfaces have been scanned. Ionization potential, electron affinity, electronegativity, global hardness and softness of the drug have been calculated. Further, drug-DNA interactions have been examined using modified second order perturbation theory along with multicentred-multipole expansion technique. Results have been discussed in the light of other theoretical and experimental observations. Efforts have been made to elucidate the binding patterns and thereby biological properties of the drug.

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

Electronic Structure Calculations of Oxygen Atom Transport Energetics in the Presence of Screw Dislocations in Tungsten

Plastic flow in body-centered cubic (bcc) alloys is governed by the thermally-activated motion of screw dislocations in close-packed planes. In bcc interstitial solid solutions, solute diffusion can occur at very fast rates owing to low migration energies and solute concentrations. Under mechanical loading, solutes may move on the same or similar time scale as dislocations glide, even at low temperatures, potentially resulting in very rich co-evolution processes that may have important effects in the overall material response. It is therefore important to accurately quantify the coupling between interstitial impurities and dislocations, so that larger-scale models can correctly account for their interactions. In this paper, we use electronic structure calculations to obtain the energetics of oxygen diffusion under stress and its interaction energy with screw dislocation cores in bcc tungsten. We find that oxygen atoms preferentially migrate from tetrahedral to tetrahedral site with an energy of 0.2 eV. This energy couples only weakly to hydrostatic and deviatoric deformations, with activation volumes of less than 0.02 and 0.02 b 3 , respectively. The strongest effect is found for the inelastic interaction between O atoms and screw dislocation cores, which leads to attractive energies between 1.2 and 1.9 eV and sometimes triggers a transformation of the screw dislocation core from an easy core configuration to a hard core configuration.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Predicting Device Parameters for Dye-Sensitized Solar Cells from Electronic Structure Calculations to Reproduce Experiment.

Given that improvements to the power-conversion efficiency (PCE) of dye-sensitized solar cells (DSSCs) have slowed in recent years, a means to accurately predict the device parameters yielded by trial dyes in silico, without having to synthesize them, would be extremely valuable to speed up the design process. Currently, the best-performing methods of calculating device parameters rely on a set of experimentally determined kinetic coefficients. In practice, it is very difficult to measure these kinetic parameters accurately, limiting the overall accuracy of such predictive methods. This work proposes a model to obtain key parameters such as J(SC), V-OC, and PCE using only the results from density functional theory (DFT) and time-dependent DFT calculations, noting that rates of electron-transfer steps are ultimately linked to the electronic structure of the dye center dot center dot center dot TiO2 working electrode. Six organic DSSC dyes from dissimilar chemical classes (L0, L1, L2, WS-2, WS-92, and C281) were chosen to demonstrate the power of this approach. Their a priori known experimentally determined device performance metrics served to validate our predictions. The greatest absolute error in our predicted PCE values was 0.36% relative to the experiment, while the greatest fractional error was 0.042. This indicates that the proposed model offers a dramatic improvement on previous predictive methods for DSSC device parameters, both in accuracy and in consistency. Moreover, such a predictive model has great potential to be applied to other photovoltaic applications, further enabling the design of novel, highly efficient photoactive materials.

density functional theory↗