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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Femtosecond X-ray Spectroscopy Directly Quantifies Transient Excited-State Mixed Valency

Quantifying charge delocalization associated with short-lived photoexcited states of molecular complexes in solution remains experimentally challenging, requiring local element specific femtosecond experimental probes of time-evolving electron transfer. In this study, we quantify the evolving valence hole charge distribution in the photoexcited charge transfer state of a prototypical mixed valence bimetallic iron–ruthenium complex, [(CN) 5 Fe II CNRu III (NH 3 ) 5 ]-, in water by combining femtosecond X-ray spectroscopy measurements with time-dependent density functional theory calculations of the excited-state dynamics. We estimate the valence hole charge that accumulated at the Fe atom to be 0.6 ± 0.2, resulting from excited-state metal-to-metal charge transfer, on an ~ 60 fs time scale. Our combined experimental and computational approach provides a spectroscopic ruler for quantifying excited-state valency in solvated complexes.

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

Simultaneous First-Order Valence and Oxygen Vacancy Order/Disorder Transitions in (Pr 0.85 Y 0.15 ) 0.7 Ca 0.3 CoO 3-δ via Analytical Transmission Electron Microscopy

Perovskite cobaltites have been studied for years as some of the few solids to exhibit thermally driven spin-state crossovers. The unanticipated first-order spin and electronic transitions recently discovered in Pr-based cobaltites are notably different from these conventional crossovers, and are understood in terms of a unique valence transition. In essence, the Pr valence is thought to spontaneously shift from 3+ toward 4+ on cooling, driving subsequent transitions in Co valence and electronic/magnetic properties. Here, we apply temperature-dependent transmission electron microscopy and spectroscopy to study this phenomenon, for the first time with atomic spatial resolution, in the prototypical (Pr 0.85 Y 0.15 )(0.70) Ca 0.30 CoO 3-δ . In addition to the direct spectroscopic observation of charge transfer between Pr and Co at the 165 K transition (on both the Pr and O edges), we also find a simultaneous order/disorder transition associated with O vacancies. Remarkably, the first-order valence change drives a transition between ordered and random O vacancies, at constant O vacancy density, demonstrating reversible crystallization of such vacancies even at cryogenic temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Metal–Ligand Covalency in the Valence Excited States of Metal Dithiolenes Revealed by S 1s3p Resonant Inelastic X-ray Scattering

Metallo dithiolene complexes with biological and catalytic relevance are well-known for having strong metal–ligand covalency, which dictates their valence electronic structures. We present the resonant sulfur Kβ (1s3p) X-ray emission spectroscopy (XES) for a series of Ni and Cu bis(dithiolene) complexes to reveal the ligand sulfur contributions to both the occupied and unoccupied valence orbitals. While S K-edge X-ray absorption spectroscopy played a critical role in identifying the covalency of the unoccupied orbitals of metal dithiolenes, the present focus on XES explores the occupied density of states. For a series of [Cu(mnt) 2 ] n– and [Ni(mnt) 2 ] n– anions and dianions, a comparison of the nonresonant and resonant S Kβ XES spectra highlights the dramatic improvement in spectral resolution and corresponding ability to differentiate subtle changes in occupied electronic structure across the series. Furthermore, the use of resonant inelastic X-ray scattering (RIXS) probes the valence excited states and the core–valence couplings of the complexes. By employing a theoretical approach based on time-dependent density functional theory to interpret the RIXS spectra, we reveal how metal–ligand covalency influences the excited state energies and covalencies. We identify the low energy excited states as having the same symmetry as the nominal “ligand field” or “d–d” states that typically dominate the photophysics of 3d metal complexes but with significant metal– ligand charge transfer character dictated by their covalency. These results suggest that strong metal–ligand covalency can be used to influence the charge-transfer photochemistry of first row transition metal complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Auger electron emission initiated by the creation of valence-band holes in graphene by positron annihilation

Auger processes involving the filling of holes in the valence band are thought to make important contributions to the low-energy photoelectron and secondary electron spectrum from many solids. However, measurements of the energy spectrum and the efficiency with which electrons are emitted in this process remain elusive due to a large unrelated background resulting from primary beam-induced secondary electrons. Here, we report the direct measurement of the energy spectra of electrons emitted from single layer graphene as a result of the decay of deep holes in the valence band. These measurements were made possible by eliminating competing backgrounds by employing low-energy positrons (<1.25 eV) to create valence-band holes by annihilation. Lastly, our experimental results, supported by theoretical calculations, indicate that between 80 and 100% of the deep valence-band holes in graphene are filled via an Auger transition.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Hierarchical nickel valence gradient stabilizes high-nickel content layered cathode materials

High-nickel content cathode materials offer high energy density. However, the structural and surface instability may cause poor capacity retention and thermal stability of them. To circumvent this problem, nickel concentration-gradient materials have been developed to enhance high-nickel content cathode materials’ thermal and cycling stability. Even though promising, the fundamental mechanism of the nickel concentration gradient’s stabilization effect remains elusive because it is inseparable from nickel’s valence gradient effect. To isolate nickel’s valence gradient effect and understand its fundamental stabilization mechanism, we design and synthesize a LiNi 0.8 Mn 0.1 Co 0.1 O 2 material that is compositionally uniform and has a hierarchical valence gradient. The nickel valence gradient material shows superior cycling and thermal stability than the conventional one. The result suggests creating an oxidation state gradient that hides the more capacitive but less stable Ni 3+ away from the secondary particle surfaces is a viable principle towards the optimization of high-nickel content cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2022

Anisotropy-driven quantum criticality in an intermediate valence system

Intermetallic compounds containing f-electron elements have been prototypical materials for investigating strong electron correlations and quantum criticality (QC). Their heavy fermion ground state evoked by the magnetic f-electrons is susceptible to the onset of quantum phases, such as magnetism or superconductivity, due to the enhanced effective mass (m*) and a corresponding decrease of the Fermi temperature. However, the presence of f-electron valence fluctuations to a non-magnetic state is regarded an anathema to QC, as it usually generates a paramagnetic Fermi-liquid state with quasiparticles of moderate m*. Such systems are typically isotropic, with a characteristic energy scale T 0 of the order of hundreds of kelvins that require large magnetic fields or pressures to promote a valence or magnetic instability. Here we show the discovery of a quantum critical behaviour and a Lifshitz transition under low magnetic field in an intermediate valence compound α-YbAlB 4 . The QC origin is attributed to the anisotropic hybridization between the conduction and localized f-electrons. These findings suggest a new route to bypass the large valence energy scale in developing the QC.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Electric-field-driven electron-transfer in mixed-valence molecules

Molecular quantum-dot cellular automata is a computing paradigm in which digital information is encoded by the charge configuration of a mixed-valence molecule. General-purpose computing can be achieved by arranging these compounds on a substrate and exploiting intermolecular Coulombic coupling. The operation of such a device relies on nonequilibrium electron transfer (ET), whereby the time-varying electric field of one molecule induces an ET event in a neighboring molecule. The magnitude of the electric fields can be quite large because of close spatial proximity, and the induced ET rate is a measure of the nonequilibrium response of the molecule. We calculate the electric-field-driven ET rate for a model mixed-valence compound. The mixed-valence molecule is regarded as a two-state electronic system coupled to a molecular vibrational mode, which is, in turn, coupled to a thermal environment. Both the electronic and vibrational degrees-of-freedom are treated quantum mechanically, and the dissipative vibrational-bath interaction is modeled with the Lindblad equation. This approach captures both tunneling and nonadiabatic dynamics. Relationships between microscopic molecular properties and the driven ET rate are explored for two time-dependent applied fields: an abruptly switched field and a linearly ramped field. In both cases, the driven ET rate is only weakly temperature dependent. When the model is applied using parameters appropriate to a specific mixed-valence molecule, diferrocenylacetylene, terahertz-range ET transfer rates are predicted.

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

A cautionary tale: Problems in the valence-CASSCF description of the ground state (X1Σ+) of BF

In the full optimized reaction space and valence-complete active space self-consistent field (vCAS) methods, a set of active orbitals is defined as the union of the valence orbitals on the atoms, all possible configurations involving the active orbitals are generated, and the orbitals and configuration coefficients are self-consistently optimized. Such wave functions have tremendous flexibility, which makes these methods incredibly powerful but can also lead to inconsistencies in the description of the electronic structure of molecules. In this paper, the problems that can arise in vCAS calculations are illustrated by calculations on the BH and BF molecules. BH is well described by the full vCAS wave function, which accounts for molecular dissociation and 2s–2p near-degeneracy in the boron atom. The same is not true for the full vCAS wave function for BF. There is mixing of core and active orbitals at short internuclear distances and swapping of core and active orbitals at large internuclear distances. In addition, the virtual 2π orbitals, which were included in the active space to account for the 2s–2p near degeneracy effect, are used instead to describe radial correlation of the electrons in the F2pπ-like pairs. Although the above changes lead to lower vCAS energies, they lead to higher vCAS+1+2 energies as well as irregularities and/or discontinuities in the potential energy curves. All of the above problems can be addressed by using the spin-coupled generalized valence bond-inspired vCAS wave function for BF, which includes only a subset of the atomic valence orbitals in the active space.

Xu, Lu T. (ORCID:0000000182064902)↗
DOE OSTI2018

Finding the hidden valence band of N = 7 armchair graphene nanoribbons with angle-resolved photoemission spectroscopy

To understand the optical and transport properties of graphene nanoribbons, an unambiguous determination of their electronic band structure is needed. In this work we demonstrate that the photoemission intensity of each valence sub-band, formed due to the quantum confinement in quasi-one-dimensional (1D) graphene nanoribbons, is a peaked function of the two-dimensional (2D) momentum. We resolve the long-standing discrepancy regarding the valence band effective mass (m* VB ) of armchair graphene nanoribbons with a width of N = 7 carbon atoms (7-AGNRs). In particular, angle-resolved photoemission spectroscopy (ARPES) and scanning tunneling spectroscopy report m* VB ≈0.2 and ≈0.4 of the free electron mass (m e ), respectively. ARPES mapping in the full 2D momentum space identifies the experimental conditions for obtaining a large intensity for each of the three highest valence 1D sub-bands. Our detail map reveals that previous ARPES experiments have incorrectly assigned the second sub-band as the frontier one. The correct frontier valence sub-band for 7-AGNRs is only visible in a narrow range of emission angles. For this band we obtain an ARPES derived effective mass of 0.4 m e , a charge carrier velocity in the linear part of the band of 0.63 x 10 6 m s -1 and an energy separation of only ≈60 meV to the second sub-band. Lastly, our results are of importance not only for the growing research field of graphene nanoribbons but also for the community, which studies quantum confined systems.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Pressure-induced changes of valence fluctuation in β - YbAlB 4 probed by x-ray absorption spectroscopy

Here we report detailed valence fluctuation phenomena in the unique quantum-critical compound β-YbAlB 4 under pressures and at low temperatures. We directly observed the drastic change in the pressure dependence of the mean Yb valence at about 3 GPa with no pressure-induced structural transition. Below 3 GPa, the anomaly in the temperature dependences of the mean Yb valence was observed at about 55 K under ambient pressure, corresponding to a previously observed reduced Kondo coherence temperature, and this temperature rapidly decreases to 22 K at 2.2 GPa, in contrast to the monotonous decrease of the high Kondo temperature (~250K at ambient pressure). The present results reveal that this reduced Kondo coherence temperature is responsible for the unconventional quantum critical behaviors in β-YbAlB 4 . Above 3 GPa, it was found that the temperature dependence of the mean Yb valence exhibits a discontinuous change at low temperature (10.5 and 9 K under 4.8 and 5.5 GPa, respectively).

36 MATERIALS SCIENCE↗
DOE OSTI2024

First-Principles Treatment of Vibrational Broadening in X-Ray Excited Valence Band Spectra for n-SrTiO 3 (001)

The valence band maximum (VBM) is an important quantity for semiconductors as it locates the Fermi level relative to the band edge. Accurate measurement of this quantity in near-surface regions of semiconductors by photoemission is a first step toward determining the electronic properties of heterostructures involving these materials. While extrapolating the leading edge of the valence band to the energy axis in photoemission spectra is a widely used way to find the VBM, this method can be ambiguous if the leading edge exhibits multiple slopes. Another way to determine the VBM is to fit the leading edge to an appropriately broadened, cross-section modulated theoretical density of states (DOS). Three kinds of broadening that should be included for maximum accuracy are those due to: (1) finite instrumental resolution, (2) valence hole lifetime, and (3) vibrational excitations. While steps (1) and (2) are straightforward to implement, (3) is more difficult because the appropriate amount of broadening is not known a priori. Here, we demonstrate that explicit inclusion of vibrational broadening using ab initio molecular dynamics facilitates accurate VBM determination for n-SrTiO 3 (001). The total DOS is constructed by summing time-averaged projections at elevated temperature onto s - , p - , and d orbitals for the constituent atoms and modulating with the associated photoemission cross sections. Subsequent convolutions of the total DOS, first with a Gaussian of width equal to the experimental energy resolution and second with a Lorentzian to simulate valence hole lifetime effects, yield line shapes that reproduce the experimental leading edges rather well. The VBM is then given by the energy at which the vibrationally broadened total DOS (prior to the convolutions) goes to zero. The VBMs generated by this method quantitatively agree with those resulting from extrapolating from the middle of the measured leading edge for SrTiO 3 .

36 MATERIALS SCIENCE↗
DOE OSTI2018

Pion and kaon valence quark distribution functions from Dyson-Schwinger equations

Using realistic quark propagators and meson Bethe-Salpeter amplitudes based on the Dyson-Schwinger equations, we calculate the pion and kaon's valence parton distribution functions (PDF) through the modified impulse approximation. The PDFs we obtained at hadronic scale have the purely valence characteristic and exhibit both dynamical chiral symmetry breaking and SU(3) flavor symmetry breaking effects. A new calculation technique is introduced to determine the valence PDFs with precision. Through next-to-leading order (NLO) evolution, our result is compared with pion and kaon valence PDF data at experimental scale. Good agreement is found in the case of pion, while deviation emerges for kaon. We point out this situation can potentially be resolved by incorporating gluon contributions into the mesons if the pion hosts more gluons than kaon nonperturbatively.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2019

Probing Ultrafast Electron (De)localization Dynamics in Mixed Valence Complexes Using Femtosecond X-ray Spectroscopy (Final Report)

The overall goal of this research program was to understand valence electron and vibrational motion following metal-to-metal charge transfer (MMCT) excitation in the mixed valence complexes dissolved in aqueous solution. The project objectives were (i) to observe the time-dependent re-arrangement of d electrons across two transition metal sites and the bridging ligand following photoinduced MMCT excitation on a sub-50 femtosecond timescale using femtosecond X-ray pulses generated at LCLS (ii) to simulate femtosecond X-ray absorption and emission spectra of solvated, photo-excited, transition metal mixed valence complexes using a realistic treatment of multi-electron correlations/transitions, spin-orbit coupling and final state lifetime effects and to propose and study the feasibility of nonlinear X-ray experiments on solvated transition metal mixed valence systems using future X-FEL light sources and (iii) to determine the role of coupled electronic and vibrational motions during ultrafast photoinduced charge transfer. The final report highlights the scientific results obtained during this funding period.

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

A Novel Feature of Valence Quark Distributions in Hadrons

Examining the evolution of the maximum of valence quark distribution, qV, weighted by Bjorken x, h(x,t)≡xqV(x,t), it is observed that h(x,t) at the peak becomes a one-parameter function; h(xp,t)=Φ(xp(t)), where xp is the position of the peak, t=logQ2, and Q2 is the resolution scale. This observation is used to derive a new model-independent relation which connects the partial derivative of the valence parton distribution functions (PDFs) in xp to the quantum chromodynamics (QCD) evolution equation through the xp derivative of the logarithm of the function Φ(xp(t)). A numerical analysis of this relation using empirical PDFs results in an observation of the exponential form of the Φ(xp(t))=h(xp,t)=CeDxp(t) for leading to next-to-next leading order approximations of PDFs for the range of Q2, covering four orders in magnitude. The exponent, D, of the observed “height-position” correlation function converges with the increase in the order of approximation. This result holds for all the PDF sets considered. A similar relation is observed also for the pion valence quark distribution, indicating that the obtained relation may be universal for any non-singlet partonic distribution. The observed “height-position” correlation is used also to indicate that no finite number of exchanges can describe the analytic behavior of the valence quark distribution at the position of the peak at fixed Q2.

Leon, Christopher↗
NASA NTRS1983

An ab initio study of core-valence correlation

Especially in the cases of the first two columns of the periodic table, the inclusion of core-valence correlation in ab initio CI calculations yields a contraction of the atomic valence shell and improves both calculated atomic ionization potentials and atomic energy separations. For the alkali dimers Na2, K2, and Rb2, the presently calculated bond lengths are in excellent agreement with experiments when core-valence is included. In addition, the valence dissociation energies are accurate.

Partridge, H.↗
NASA NTRS2004

Oxygen Fugacity of Mare Basalts and the Lunar Mantle Application of a New Microscale Oxybarometer Based on the Valence State of Vanadium

The ability to estimate oxygen fugacities for mare basalts and to extend these observations to the lunar mantle is limited using bulk analysis techniques based on buffering assemblages or the valence state of iron. These limitations are due to reequilibration of mineral assemblages at subsolidus conditions, deviations of mineral compositions from thermodynamic ideality, size requirements, and the limits of the iron valence at very low fO2. Still, these approaches have been helpful and indicate that mare basalts crystallized at fO2 between the iron-w stite buffer (IW) and the ilmenite breakdown reaction (ilmenite = rutile + iron). It has also been inferred from these estimates that the lunar mantle is also highly reduced lying at conditions below IW. Generally, these data cannot be used to determine if the mare basalts become increasingly reduced during transport from their mantle source and eruption at the lunar surface and if there are differences in fO2 among mare basalts or mantle sources. One promising approach to determining the fO2 of mare basalts is using the mean valence of vanadium (2+, 3+, 4+, 5+) determined on spots of a few micrometers in diameter using synchrotron x-ray absorption fine structure (XAFS) spectroscopy. The average valence state of V in basaltic glasses is a function of fO2, temperature, V coordination, and melt composition. Here, we report the initial results of this approach applied to lunar pyroclastic glasses.

Shearer, C. K.↗
NASA NTRS2011

Molybdenum Valence in Basaltic Silicate Melts: Effects of Temperature and Pressure

The metal-silicate partitioning behavior of molybdenum has been used as a test for equilibrium core formation hypotheses [for example, 1-6]. However, current models that apply experimental data to equilibrium core-mantle differentiation infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Molybdenum, a multi-valent element with a valence transition near the fO2 of interest for core formation (approx.IW-2) will be sensitive to changes in fO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo(6+) can be either octahedrally or tetrahedrally coordinated. Here we present X-ray absorption near edge structure (XANES) measurements of Mo valence in basaltic run products at a range of P, T, and fO2 and further quantify the valence transition of Mo.

Danielson, L. R.↗
DOE OSTI2023

Measuring the Neutron Spin Asymmetry A1n in the Valence Quark Region in Hall C at Jefferson Lab

The quest to understand how the nucleon spin is decomposed into its constituent quark and gluon spin and orbital angular momentum (OAM) components has been at the forefront of nuclear physics for decades. Due to the non-perturbative nature of Quantum Chromodynamics (QCD) - the theory describing how quarks and gluons bind together to form protons and neutrons - making absolute predictions of nucleon spin structure is generally difficult, especially as a function of its quark and gluon longitudinal momentum fraction x. Measurements involving nucleon spin structure serve as a sensitive test for QCD, including ab-initio lattice QCD calculations due to the advent of the quasi-PDF formalism, and various predictions that diverge at large-x. The neutron spin asymmetry An 1 at high?x is a key observable for probing nucleon spin structure. In the valence domain (x > 0.5), sea effects are expected to be negligible, and so the total nucleon spin is considered to be carried by the valence quarks. The valence region can therefore enable us to study the role of quark OAM and other non-perturbative effects of the strong force. An 1 was measured in the deep inelastic scattering region of 0.40 < x < 0.75 and 6 < Q2 < 10 GeV2 in Hall C at Jefferson Lab using a 10.4 GeV longitudinally polarized electron beam, upgraded polarized 3He target, and the High Momentum Spectrometer (HMS) and Super High Momentum Spectrometer (SHMS). E12- 06-110 provides the first precision data in the valence quark region above x = 0.60, and its preliminary results proved consistent with earlier data disqualifying a pQCD model that excluded quark OAM. Combined with previous world proton data, the ratio of the polarized-to-unpolarized up quark momentum distribution (?u + ?u)/(u + u) remained positive at large-x, and the down quark (?d + ?d)/(d + d) remained negative.

Rehfuss, Melanie↗