SEARCH · Engineering Papers

Results for “valence bands”

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.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 505 records · Page 28

All sources NASA NTRS DOE OSTI

NASA NTRS1990

Medium resolution studies of extreme ultraviolet emission from N2 by electron impact - The effect of predissociation on the emission cross section of the b 1Pi(u) state

The electron impact induced fluorescence spectrum of N2 is measured in the 102-134 nm range at a 0.05 nm spectral resolution. The spectral measurements provide the emission cross sections of the transitions of the b 1Pi(u)-X 1Sigma(+)g Birge-Hopfield I-band system. The structure and vibrational population distribution of this system are strongly affected by a configuration interaction of the valence b 1Pi(u) and Rydberg c 1Pi(u) and o 1Pi(u) states. The excitation function (0-400 eV) for the b-X (1,2) transition is measured and a modified Born approximation analytic model is applied to calculate the oscillator strength for the b 1Pi(u)-X band system. With the exception of the v-prime = 1 level, vibrational levels of the b 1Pi(u) state predissociate with a branching ratio of between 0.95 and 1.00. Predissociation of the b 1Pi(u) state contributes approximately six percent of the total dissociation cross section of N2 by electron impact at 100 eV.

James, Geoffrey K.↗

DOE OSTI2023

Effect of Fermi surface topology change on the Kagome superconductor CeRu 2 under pressure

The cubic Laves phase compound CeRu 2 with a Kagome substructure of Ru has been investigated to understand myriad fascinating phenomena resulting from competition among its various physical and geometric features. Such phenomena include flat bands, van Hove singularities, Dirac cones, reentrant superconductivity, magnetism, the Fulde–Ferrell–Larkin–Ovchinnikov state, valence fluctuations, time-irreversible anisotropic s-state superconductivity, etc. Extensive studies have thus been carried out since 1958 when the highly unusual coexistence of superconductivity and ferromagnetism was proposed for the mixed compounds (Ce,Gd)Ru 2 . Activity has accelerated in recent years due to increasing interest in topological states in superconductors. However, there has been little investigation of the mutual influence of these fascinating states. Therefore, we systematically investigated the superconductivity and possible Fermi surface topological change in CeRu 2 via magnetic, resistivity, and structural measurements under pressure up to ~168 GPa. An unusual phase diagram that suggests an intriguing interplay between the compound’s superconducting order and Fermi surface topological order has been constructed. A resurgence in its superconducting transition temperature was observed above 28 GPa. Our experiments have identified a structural transition above 76 GPa and a few tantalizing phase transitions driven by high pressure. Our high-pressure results further suggest that superconductivity and Fermi surface topology in CeRu 2 are strongly intertwined.

36 MATERIALS SCIENCE↗

NASA NTRS1996

Electronic Structure of TIBa(sub 2)CaCu(sub 2)O(sub 7-delta)

The core levels of TIBa(sub 2)CaCu(sub 2)O(sub 7-delta) epitaxial films have been measured with x-ray photoelectron spectroscopy (XPS). The valence electronic structure has been determined using the full-potential linear muffin tin orbital band structure method and measured with XPS.

Epitaxial films van Hove Fermi level↗

DOE OSTI2025

Topological Mixed Valence Model for Twisted Bilayer Graphene

Song and Bernevig (SB) have recently proposed a topological heavy-fermion description of the physics of magic angle twisted bilayer graphene (MATBG), involving the hybridization of flat-band electrons with a relativistic conduction sea. Here, we explore the consequences of this model, seeking a synthesis of understanding drawn from heavy-fermion physics and MATBG experiments. Our work identifies a key discrepancy between measured and calculated on-site Coulomb interactions, implicating renormalization effects that are not contained in the current model. With these considerations in mind, we consider a SB model with a single, renormalized on-site interaction between the f electrons, containing a phenomenological heavy-fermion binding potential on the moiré A A sites. This feature allows the simplified model to capture the periodic reset of the chemical potential with filling and the observed stability of local moment behavior. We argue that a two-stage Kondo effect will develop in MATBG as a consequence of the relativistic conduction band: Kondo I occurs at high temperatures, establishing a coherent hybridization at the Γ points and a non-Fermi liquid of incoherent fermions at the moiré K points; at much lower temperatures, Kondo II leads to a Fermi liquid in the flat band. Utilizing an auxiliary-rotor approach, we formulate a mean-field treatment of MATBG that captures this physics, describing the evolution of the normal state across a full range of filling factors. By contrasting the relative timescales of phonons and valence fluctuations in bulk heavy-fermion materials with that of MATBG, we are led to propose a valley-polaron origin to the Coulomb renormalization and the heavy-fermion binding potential identified from experiment. We also discuss the possibility that the two-fluid, non-Fermi liquid physics of the relativistic Kondo lattice is responsible for the strange-metal physics observed in MATBG. Published by the American Physical Society 2025

Lau, Liam L. H. (ORCID:0000000166039088)↗

DOE OSTI2022

Electronic and magnetic properties of the topological semimetal SmMg 2 Bi 2

Dirac semimetals show nontrivial physical properties and can host exotic quantum states like Weyl semimetals and topological insulators under suitable external conditions. Here, by combining angle-resolved photoemission spectroscopy measurements (ARPES) and first-principle calculations, we demonstrate that the Zintl-phase compound SmMg 2 Bi 2 is in close proximity to a topological Dirac semimetallic state. ARPES results show a Dirac-like band crossing at the zone center near the Fermi level (E F ), which is further confirmed by first-principle calculations. Theoretical studies also reveal that SmMg 2 Bi 2 belongs to a Z 2 topological class and hosts spin-polarized states around the E F . Zintl's theory predicts that the valence state of Sm in this material should be Sm 2+ , however, we detect many Sm-4f multiplet states (flat-bands) whose energy positions and relative intensities suggest the presence of both dominant Sm 2+ and minor Sm 3+ . The small concentration (2.5%) of Sm 3+ in the bulk of a crystal is inferred to arise from Sm vacancies in the crystal. It is also evident that these flat bands and other dispersive states are strongly hybridized when they cross each other. Due to the presence of Sm 3+ ions, the temperature dependence of the magnetic susceptibility χ (T) shows a Curie-Weiss-like contribution in the low-temperature region, in addition to the Van Vleck-like behavior expected for the Sm 2+ ions. The present study will help to better understand the electronic structure, magnetism, and transport properties of related materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2026

Unconventional polaronic ground state in superconducting LiTi 2 O 4

Geometrically frustrated lattices can display a range of correlated phenomena, ranging from spin frustration and charge order to dispersionless flat bands due to quantum interference. One particularly compelling family of such materials is the half-valence spinel LiB 2 O 4 materials. On the B-site frustrated pyrochlore sublattice, the interplay of correlated metallic behavior and charge frustration leads to a superconducting state in LiTi 2 O 4 and heavy fermion behavior in LiV 2 O 4 . To date, however, LiTi 2 O 4 has primarily been understood as a conventional BCS superconductor despite a lattice structure that could host more exotic ground states. Here, we present a multimodal investigation of LiTi 2 O 4 , combining ARPES, RIXS, proximate magnetic probes, and ab-initio many-body theoretical calculations. Our data reveals a novel mobile polaronic ground state with spectroscopic signatures that underlie co-dominant electron-phonon coupling and electron-electron correlations also found in the lightly doped cuprates. The cooperation between the two interaction scales distinguishes LiTi 2 O 4 from other superconducting titanates, suggesting an unconventional origin to superconductivity in LiTi 2 O 4 . Our work deepens our understanding of the rare interplay of electron-electron correlations and electron-phonon coupling in unconventional superconducting systems. In particular, our work identifies the geometrically frustrated, mixed-valence spinel family as an under-explored platform for discovering unconventional, correlated ground states.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Extending the Gutzwiller approximation to intersite interactions

In this work, we develop an extension of the Gutzwiller approximation (GA) formalism that includes the effects of Coulomb interactions of arbitrary range (including density density, exchange, pair hopping, and Coulomb-assisted hopping terms). This formalism reduces to the ordinary GA formalism for the multiband Hubbard models in the presence of only local interactions. This is accomplished by combining the 1 / z expansion—where z is the coordination number, and only the leading-order terms contribute in the limit of infinite dimensions—with a P R † P R - I expansion, where P R is the Gutzwiller projector on the site R . Furthermore, the method is conveniently formulated in terms of a Gutzwiller Lagrange function. We apply our theory to the extended single-band Hubbard model. Similarly to the usual Brinkman-Rice mechanism, we find a Mott transition. A valence skipping transition is observed, where the occupation of the empty and doubly occupied states for the Gutzwiller wave function is enhanced with respect to the uncorrelated Slater determinant wave function.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2025

An Experimental and Theoretical Study of the Valence Shell Electronic Structure of Nitromethane

Vibrationally resolved CH 3 NO 2 and CD 3 NO 2 photoelectron spectra and angular distribution parameters, β, have been measured in the photon energy range 20–80 eV. This allows a comprehensive investigation of conflicting literature interpretations of the two outermost photoelectron bands, complemented by high-level calculations characterizing the three O lone-pair-based orbital ionizations expected in this region. Franck–Condon simulations allow the regular vibrational progressions observed at the beginning of the first and second bands to be assigned as predominantly modes v 5 and v 6 of the D 0 and D 2 cation states, respectively. Irregular structuring observed midband in both bands is attributed to avoided crossings between the adiabatic D 0 /D 1 and D 1 /D 2 states as identified in potential surface cuts taken along the v 5 and v 6 normal mode coordinates. The associated D 0 /D 1 and D 1 /D 2 conical intersections were located and characterized, allowing possible vibronic coupling and its impact on the photoelectron spectra of the D 0 , D 1 , and D 2 states to be discussed. This helps rationalize the apparently missing D 1 ionization in this region, although some contribution by this state may be identifiable in the β-parameter spectra. Theoretical analysis of the complete valence region spectrum identifies the early breakdown of the independent electron model beyond these first two bands.

Powis, Ivan [University of Nottingham (United King↗

DOE OSTI2019

Crystal Chemistry, Band-Gap Red Shift, and Electrocatalytic Activity of Iron-Doped Gallium Oxide Ceramics

This work for the first time unfurls the fundamental mechanisms and set the stage for an approach to derive electrocatalytic activity, which is otherwise not possible, in a traditionally known wide band gap oxide material. Specifically, we report on the tunable optical properties, in terms of wide spectral selectivity and red-shifted band gap, and electrocatalytic behavior of iron (Fe) doped gallium oxide (ß-Ga 2 O 3 ) model system. X-ray diffraction (XRD) studies of sintered Ga 2-x Fe x O 3 (GFO) (0.0 ≤ x ≤ 0.3) compounds provide evidence for the Fe 3+ substitution at Ga 3+ site without any secondary phase formation. Rietveld refinement of XRD patterns reveal that the GFO compounds crystallize in monoclinic crystal symmetry with C2/m space group. The electronic structure of the GFO compounds probed using X-ray photoelectron spectroscopy data reveals that, at lower concentrations of Fe exhibits mixed chemical valence states (Fe 3+ , Fe 2+ ), whereas single chemical valence state (Fe 3+ ) is evident for higher Fe content (x = 0.20-0.30). The optical absorption spectra reveal a significant red shift in the optical band gap with Fe doping. The origin of the significant red shift even at low concentrations of Fe (x = 0.05) is attributed to the strong sp-d exchange interaction originated from the 3 d 5 electrons of Fe 3+ . The optical absorption edge observed at ˜450 nm with lower intensity is the characteristic of Fe doped compounds associated with Fe 3+ - Fe 3+ double excitation process. Coupled with optical band gap red shift, electrocatalytic studies of GFO compounds reveals that, interestingly, Fe doped Ga 2 O 3 compound exhibits electrocatalytic activity in contrast to intrinsic Ga 2 O 3 . Fe doped samples (GFO) demonstrated appreciable electrocatalytic activity towards the generation of H 2 through electrocatalytic water splitting. An onset potential and tafel slope of GFO compounds includes: ~900 mV, ~210 mVdec -1 (x = 0.15) and ~1036 mV, ~290 mVdec-1 (x = 0.30). The electrocatalytic activity of Fe doped Ga-oxide compounds is attributed to cumulative effect of different mechanisms such as; doping resulted new catalytic centers, enhanced conductivity and electron mobility. Hence, in this report, for the first time, we explored a new pathway; electrocatalytic behavior of Fe doped Ga 2 O 3 resulted due to Fe chemical states, red shift in optical band gap. The implications derived from this work may be applicable to a large class of compounds and further options may be available to design functional materials for electrocatalytic energy production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Engineering Band Gap and Photoconduction in Semiconducting Metal Organic Frameworks: Metal Node Effect

We report a systematic study on the correlation of the metal nodes in M-THQ conducting MOFs (M = Fe, Ni, Cu and Zn; THQ = tetra-hydroxybenzoquinone) with their structure, photophysical property, and photoconductivity. We found that structural preference in these MOFs is controlled by metal node identity where Cu prefers a square planar coordination which leads to a 2D Kagome type structure. Fe, Ni and Zn prefer an octahedral sphere which leads to a 3D structure. Fe-THQ has the smallest band gap and highest photoconduction as well as a long-lived ligand to metal charge transfer state due to the mixed valence state revealed by time resolved optical and X-ray absorption and tera hertz spectroscopy. Furthermore, these results demonstrate the importance of the metal node in tuning the photophysical and photocatalytic properties of MOFs.

14 SOLAR ENERGY↗

DOE OSTI2021

Mapping wave packet bifurcation at a conical intersection in CH 3 I by attosecond XUV transient absorption spectroscopy

Extreme ultraviolet (XUV) transient absorption spectroscopy has emerged as a sensitive tool for mapping the real-time structural and electronic evolution of molecules. Here, attosecond XUV transient absorption is used to track dynamics in the A-band of methyl iodide (CH 3 I). Gaseous CH 3 I molecules are excited to the A-band by a UV pump (277 nm, ~20 fs) and probed by attosecond XUV pulses targeting iodine I(4d) core-to-valence transitions. Owing to the excellent temporal resolution of the technique, passage through a conical intersection is mapped through spectral signatures of nonadiabatic wave packet bifurcation observed to occur at 15 ± 4 fs following UV photoexcitation. The observed XUV signatures and time dynamics are in agreement with previous simulations [H. Wang, M. Odelius, and D. Prendergast, J. Chem. Phys. 151, 124106 (2019)]. Furthermore, due to the short duration of the UV pump pulse, coherent vibrational motion in the CH 3 I ground state along the C-I stretch mode (538 ± 7 cm -1 ) launched by resonant impulsive stimulated Raman scattering and dynamics in multiphoton excited states of CH 3 I are also detected.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Pines’ demon observed as a 3D acoustic plasmon in Sr2RuO4

Abstract The characteristic excitation of a metal is its plasmon, which is a quantized collective oscillation of its electron density. In 1956, David Pines predicted that a distinct type of plasmon, dubbed a ‘demon’, could exist in three-dimensional (3D) metals containing more than one species of charge carrier 1 . Consisting of out-of-phase movement of electrons in different bands, demons are acoustic, electrically neutral and do not couple to light, so have never been detected in an equilibrium, 3D metal. Nevertheless, demons are believed to be critical for diverse phenomena including phase transitions in mixed-valence semimetals 2 , optical properties of metal nanoparticles 3 , soundarons in Weyl semimetals 4 and high-temperature superconductivity in, for example, metal hydrides 3,5–7 . Here, we present evidence for a demon in Sr 2 RuO 4 from momentum-resolved electron energy-loss spectroscopy. Formed of electrons in the β and γ bands, the demon is gapless with critical momentum q c = 0.08 reciprocal lattice units and room-temperature velocity v = (1.065 ± 0.12) × 10 5 m s −1 that undergoes a 31% renormalization upon cooling to 30 K because of coupling to the particle–hole continuum. The momentum dependence of the intensity of the demon confirms its neutral character. Our study confirms a 67-year old prediction and indicates that demons may be a pervasive feature of multiband metals.

Science & Technology - Other Topics↗

DOE OSTI2022

The non-centrosymmetric layered compounds IrTe 2 I and RhTe 2 I

The previously unreported layered compounds IrTe 2 I and RhTe 2 I were prepared by a high-pressure synthesis method. Single crystal X-ray and powder X-ray diffraction studies find that the compounds are isostructural, crystallizing in a layered orthorhombic structure in the non-centrosymmetric, non-symmorphic space group Pca2 1 (#29). Characterization reveals diamagnetic, high resistivity, semiconducting behavior for both compounds, consistent with the +3 chemical valence and d 6 electronic configurations for both iridium and rhodium and the Te–Te dimers seen in the structural study. Finally, electronic band structures are calculated for both compounds, showing good agreement with the experimental results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Prediction of exotic magnetic states in the alkali-metal quasi-one-dimensional iron selenide compound Na 2 FeSe 2

The magnetic and electronic phase diagram of a model for the quasi-one-dimensional alkali-metal iron selenide compound Na 2 FeSe 2 is presented. The novelty of this material is that the valence of iron is Fe 2+ , contrary to most other iron-chain compounds with valence Fe 3+ . Using first-principles techniques, we developed a three-orbital tight-binding model that reproduces the ab initio band structure near the Fermi level. Including Hubbard and Hund couplings and studying the model via the density-matrix renormalization group and Lanczos methods, we constructed the ground-state phase diagram. A robust region where the block state ↑↑↓↓↑↑↓↓ is stabilized was unveiled. The analog state in iron ladders, employing 2×2 ferromagnetic blocks, is by now well established, but in chains a block magnetic order has not been observed yet in real materials. The phase diagram also contains a large region of canonical staggered spin order ↑↓↑↓↑↓↑ at very large Hubbard repulsion. At the block-to-staggered transition region, an exotic phase is stabilized with a mixture of both states: an inhomogeneous orbital-selective charge density wave with the exotic spin configuration ↑↑↓↑↓↓↑↓. Our predictions for Na 2 FeSe 2 may guide crystal growers and neutron-scattering experimentalists towards the realization of block states in one-dimensional iron selenide chain materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

NASA NTRS1977

Cluster calculation of carbon monoxide on a Cu surface using the self-consistent-field-X-alpha-scattered-wave method

Two geometries of CO chemisorbed on a Cu(100) surface have been studied using the self-consistent-field-X-alpha-scattered-wave method. Both geometries assume the CO molecule is bonded to the Cu surface with the C end down; one geometry is in the fourfold-symmetric hole site and one is directly on top of a Cu atom. The calculated valence density of states for the fourfold-symmetry case gives a satisfactory interpretation of the two main peaks below the copper d band in the UV photoemission spectra (UPS). A third weaker peak of the UPS data can be correlated with a CO molecule adsorbed directly on top of a copper atom.

Yu, H. L.↗

DOE OSTI2023

Synthesis and Crystal Structure of the Zintl Phases NaSrSb, NaBaSb and NaEuSb

This work details the synthesis and the crystal structures of the ternary compounds NaSrSb, NaBaSb and NaEuSb. They are isostructural and adopt the hexagonal ZrNiAl-type structure (space group P6¯2m; Pearson code hP9). The structure determination in all three cases was performed using single-crystal X-ray diffraction methods. The structure features isolated Sb3– anions arranged in layers stacked along the crystallographic c-axis. In the interstices, alkali and alkaline-earth metal cations are found in tetrahedral and square pyramidal coordination environments, respectively. The formal partitioning of the valence electrons adheres to the valence rules, i.e., Na+Sr2+Sb3–, Na+Ba2+Sb3– and Na+Eu2+Sb3– can be considered as Zintl phases with intrinsic semiconductor behavior. Electronic band structure calculations conducted for NaBaSb are consistent with this notion and show a direct gap of approx. 0.9 eV. Additionally, the calculations hint at possible inverted Dirac cones, a feature that is reminiscent of topological quantum materials.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Coupled valence carrier and core-exciton dynamics in WS 2 probed by few-femtosecond extreme ultraviolet transient absorption spectroscopy

Few-femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy, performed with optical 500-1000 nm supercontinuum and broadband XUV pulses (30-50 eV), simultaneously probes dynamics of photoexcited carriers in WS$_{2}$ at the W O$_3$ edge (37-45 eV) and carrier-induced modifications of core-exciton absorption at the W N$_{6,7}$ edge (32-37 eV). Access to continuous core-to-conduction band absorption features and discrete core-exciton transitions in the same XUV spectral region in a semiconductor provides a novel means to investigate the effect of carrier excitation on core-exciton dynamics. The core-level transient absorption spectra, measured with either pulse arriving first to explore both core-level and valence carrier dynamics, reveal that core-exciton transitions are strongly influenced by the photoexcited carriers. A $1.2\pm0.3$ ps hole-phonon relaxation time and a $3.1\pm0.4$ ps carrier recombination time are extracted from the XUV transient absorption spectra from the core-to-conduction band transitions at the W O$_{3}$ edge. Global fitting of the transient absorption signal at the W N$_{6,7}$ edge yields $\sim 10$ fs coherence lifetimes of core-exciton states and reveals that the photoexcited carriers, which alter the electronic screening and band filling, are the dominant contributor to the spectral modifications of core-excitons and direct field-induced changes play a minor role. This work provides a first look at the modulations of core-exciton states by photoexcited carriers and advances our understanding of carrier dynamics in metal dichalcogenides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2022

Electronically-coupled redox centers in trimetallic cobalt complexes

Synthesis and isolation of molecular building blocks of metal–organic frameworks (MOFs) can provide unique opportunities for characterization that would otherwise be inaccessible due to the heterogeneous nature of MOFs. Herein, we report a series of trinuclear cobalt complexes incorporating dithiolene ligands, triphenylene-2,3,6,7,10,11-hexathiolate (THT) (1 3+ ), and benzene hexathiolate (BHT) (2 3+ ), with 1,1,1,-tris(diphenylphosphinomethyl)ethane (triphos) employed as the capping ligand. Single crystal X-ray analyses of 1 3+ and 2 3+ display three five-coordinate cobalt centers bound to the triphos and dithiolene ligands in a distorted square pyramidal geometry. Cyclic voltammetry studies of 1 3+ and 2 3+ reveal three redox features associated with the formation of mixed valence states due to the sequential reduction of the redox-active metal centers (Co III/II ). Using this electrochemical data, the comproportionality values were determined for 1 and 2 (log K c = 1.4 and 1.5 for 1, and 4.7 and 5.8 for 2), suggesting strong resonance-stabilized coupling of the metal centers, with stronger electronic coupling observed for complex 2 compared to that for complex 1. Cyclic voltammetry studies were also performed in solvents of varying polarity, whereupon the difference in the standard potentials (ΔE 1/2 ) for 1 and 2 was found to shift as a function of the polarity of the solvent, indicating a negative correlation between the dielectric constant of the electrochemical medium and the stability of the mixed valence species. Spectroelectrochemical studies of in situ generated multi-valent (MV) states of complexes 1 and 2 display characteristic NIR intervalence charge transfer (IVCT) bands, and analysis of the IVCT transitions for complex 2 suggests a weakly coupled class II multi-valent species and relatively large electronic coupling factors (1700 cm –1 for the first multi-valent state of 2 2+ , and 1400 and 4000 cm –1 for the second multi-valent state of 2 + ). Here, density functional theory (DFT) calculations indicate a significant deviation in relative energies of the frontier orbitals of complexes 1 3+ , 2 3+ , and 3 + that contrasts those calculated for the analogous trinuclear cobalt dithiolene complexes employing pentamethylcyclopentadienyl (Cp*) as the capping ligand (Co 3 Cp* 3 THT and Co 3 Cp* 3 BHT, respectively), and may be a result of the cationic nature of complexes 1 3+ , 2 3+ , and 3 + .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗