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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Ferricyanide photo-aquation pathway revealed by combined femtosecond Kβ main line and valence-to-core x-ray emission spectroscopy

Reliably identifying short-lived chemical reaction intermediates is crucial to elucidate reaction mechanisms but becomes particularly challenging when multiple transient species occur simultaneously. Here, we report a femtosecond x-ray emission spectroscopy and scattering study of the aqueous ferricyanide photochemistry, utilizing the combined Fe Kβ main and valence-to-core emission lines. Following UV-excitation, we observe a ligand-to-metal charge transfer excited state that decays within 0.5 ps. On this timescale, we also detect a hitherto unobserved short-lived species that we assign to a ferric penta-coordinate intermediate of the photo-aquation reaction. We provide evidence that bond photolysis occurs from reactive metal-centered excited states that are populated through relaxation of the charge transfer excited state. Beyond illuminating the elusive ferricyanide photochemistry, these results show how current limitations of Kβ main line analysis in assigning ultrafast reaction intermediates can be circumvented by simultaneously using the valence-to-core spectral range.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Revealing core-valence interactions in solution with femtosecond X-ray pump X-ray probe spectroscopy

Abstract Femtosecond pump-probe spectroscopy using ultrafast optical and infrared pulses has become an essential tool to discover and understand complex electronic and structural dynamics in solvated molecular, biological, and material systems. Here we report the experimental realization of an ultrafast two-color X-ray pump X-ray probe transient absorption experiment performed in solution. A 10 fs X-ray pump pulse creates a localized excitation by removing a 1 s electron from an Fe atom in solvated ferro- and ferricyanide complexes. Following the ensuing Auger–Meitner cascade, the second X-ray pulse probes the Fe 1 s → 3 p transitions in resultant novel core-excited electronic states. Careful comparison of the experimental spectra with theory, extracts +2 eV shifts in transition energies per valence hole, providing insight into correlated interactions of valence 3 d with 3 p and deeper-lying electrons. Such information is essential for accurate modeling and predictive synthesis of transition metal complexes relevant for applications ranging from catalysis to information storage technology. This study demonstrates the experimental realization of the scientific opportunities possible with the continued development of multicolor multi-pulse X-ray spectroscopy to study electronic correlations in complex condensed phase systems.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2018

High selectivity of CO 2 hydrogenation to CO by controlling the valence state of nickel using perovskite

The selectivity of CO 2 hydrogenation can be significantly tuned by controlling the valence state of nickel using lanthanum-iron-nickel perovskites. Nickel with higher valence states weakens the binding of CO and increases the activation barrier for further CO hydrogenation, leading to a higher CO selectivity than the metallic nickel.

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

Resonance signatures in the body-frame valence photoionization of CF 4

Here, we present a combined experimental and theoretical investigation of the electron dynamics and body-frame angular dependence of valence photo-single ionization of CF 4 and subsequent dissociation into CF 3 + and F. Ionization from a valence t 2 orbital shows overlapping shape resonances close to threshold that couple to the same total symmetry, leading to striking changes in the photoelectron angular distributions when viewed in the body-frame.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Valence band offset at Al{sub 2}O{sub 3}/In{sub 0.17}Al{sub 0.83}N interface formed by atomic layer deposition

The valence band offset, {Delta}E{sub V}, at an Al{sub 2}O{sub 3}/In{sub 0.17}Al{sub 0.83}N interface formed by atomic layer deposition was measured by x-ray photoelectron spectroscopy. The conventional method of using the core level separation, {Delta}E{sub CL}, between O 1s and In 4d resulted in {Delta}E{sub V} = 1.3 eV, which was apparently consistent with the direct observation of the valence band edge varying the photoelectron exit angle, {theta}. However, {Delta}E{sub CL} and full width at half maximum of core-level spectra were dependent on {theta}, which indicated significant potential gradients in Al{sub 2}O{sub 3} and InAlN layers. An actual {Delta}E{sub V} of 1.2 eV was obtained considering the potential gradients.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

Interfacial chemistry and valence band offset between GaN and Al{sub 2}O{sub 3} studied by X-ray photoelectron spectroscopy

The interface region between Ga-face n-type GaN and Al{sub 2}O{sub 3} dielectric (achieved via atomic-layer deposition or ALD) is investigated by X-ray photoelectron spectroscopy (XPS). An increase in the Ga-O to Ga-N bond intensity ratio following Al{sub 2}O{sub 3} deposition implies that the growth of an interfacial gallium sub-oxide (GaO{sub x}) layer occurred during the ALD process. This finding may be ascribed to GaN oxidation, which may still happen following the reduction of a thin native GaO{sub x} by trimethylaluminum (TMA) in the initial TMA-only cycles. The valence band offset between GaN and Al{sub 2}O{sub 3}, obtained using both core-level and valence band spectra, is found to vary with the thickness of the deposited Al{sub 2}O{sub 3}. This observation may be explained by an upward energy band bending at the GaN surface (due to the spontaneous polarization induced negative bound charge on the Ga-face GaN) and the intrinsic limitation of the XPS method for band offset determination.

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

Valence states and electronic structures of Co and Mn substituted spin gapless semiconductor PbPdO{sub 2}

Electronic structures of Pb(Pd{sub 0.9}T{sub 0.1})O{sub 2} (T = Mn, Co) spin gapless semiconductors have been investigated by employing soft X-ray absorption spectroscopy (XAS) and photoemission spectroscopy (PES). The valence states of Co and Mn ions are found to be mixed-valent (∼2.7) and tetravalent, respectively. The measured valence-band PES and O 1s XAS spectra show that both PbPdO{sub 2} and PbPd{sub 0.9}Co{sub 0.1}O{sub 2} are small-gap semiconductors. This finding is supported by the calculated band structures, obtained in the density functional theory with the modified Becke-Johnson potential (mBJ) scheme. This work also shows evidence for the existence of the phase separation in Mn-substituted PbPd{sub 0.9}Mn{sub 0.1}O{sub 2}.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Research Update: Retardation and acceleration of phase separation evaluated from observation of imbalance between structure and valence in LiFePO{sub 4}/FePO{sub 4} electrode

LiFePO{sub 4} is a potential positive electrode material for lithium ion batteries. We have experimentally observed an imbalance between the valence change of Fe ions and the structure change from the LiFePO{sub 4} phase to the FePO{sub 4} phase during delithiation by simultaneous in situ XRD and XANES measurements in an LiFePO{sub 4}/FePO{sub 4} electrode. The ratio of structure change to valence change clearly indicates that the phase separation from LiFePO{sub 4} to FePO{sub 4} is suppressed at the beginning of delithiation, while it is accelerated at the latter stage, which is due to the coherent strain caused by the lattice misfit between the two phases.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Testing time-dependent density functional theory with depopulated molecular orbitals for predicting electronic excitation energies of valence, Rydberg, and charge-transfer states and potential energies near a conical intersection

Kohn-Sham (KS) time-dependent density functional theory (TDDFT) with most exchange-correlation functionals is well known to systematically underestimate the excitation energies of Rydberg and charge-transfer excited states of atomic and molecular systems. To improve the description of Rydberg states within the KS TDDFT framework, Gaiduk et al. [Phys. Rev. Lett. 108, 253005 (2012)] proposed a scheme that may be called HOMO depopulation. In this study, we tested this scheme on an extensive dataset of valence and Rydberg excitation energies of various atoms, ions, and molecules. It is also tested on a charge-transfer excitation of NH{sub 3}-F{sub 2} and on the potential energy curves of NH{sub 3} near a conical intersection. We found that the method can indeed significantly improve the accuracy of predicted Rydberg excitation energies while preserving reasonable accuracy for valence excitation energies. However, it does not appear to improve the description of charge-transfer excitations that are severely underestimated by standard KS TDDFT with conventional exchange-correlation functionals, nor does it perform appreciably better than standard TDDFT for the calculation of potential energy surfaces.

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

Site-specific intermolecular valence-band dispersion in α-phase crystalline films of cobalt phthalocyanine studied by angle-resolved photoemission spectroscopy

The valence band structure of α-phase crystalline films of cobalt phthalocyanine (CoPc) grown on Au(111) is investigated by using angle-resolved photoemission spectroscopy (ARPES) with synchrotron radiation. The photo-induced change in the ARPES peaks is noticed in shape and energy of the highest occupied molecular orbital (HOMO, C 2p) and HOMO-1 (Co 3d) of CoPc, and is misleading the interpretation of the electronic properties of CoPc films. From the damage-free normal-emission ARPES measurement, the clear valence-band dispersion has been first observed, showing that orbital-specific behaviors are attributable to the interplay of the intermolecular π-π and π-d interactions. The HOMO band dispersion of 0.1 eV gives the lower limit of the hole mobility for α-CoPc of 28.9 cm{sup 2} V{sup −1} s{sup −1} at 15 K. The non-dispersive character of the split HOMO-1 bands indicates that the localization of the spin state is a possible origin of the antiferromagnetism.

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

Electronic structure and thermoelectric properties of half-Heusler compounds with eight electron valence count—KScX (X = C and Ge)

Electronic band structure and structural properties of two representative half-Heusler (HH) compounds with 8 electron valence count (VC), KScC and KScGe, have been studied using first principles methods within density functional theory and generalized gradient approximation. These systems differ from the well studied class of HH compounds like ZrNiSn and ZrCoSb which have VC = 18 because of the absence of d electrons of the transition metal atoms Ni and Co. Electronic transport properties such as Seebeck coefficient (S), electrical conductivity (σ), electronic thermal conductivity (κ{sub e}) (the latter two scaled by electronic relaxation time), and the power factor (S{sup 2}σ) have been calculated using semi-classical Boltzmann transport theory within constant relaxation time approximation. Both the compounds are direct band gap semiconductors with band extrema at the X point. Their electronic structures show a mixture of heavy and light bands near the valance band maximum and highly anisotropic conduction and valence bands near the band extrema, desirable features of good thermoelectric. Optimal p- or n-type doping concentrations have been estimated based on thermopower and maximum power factors. The optimum room temperature values of S are ∼1.5 times larger than that of the best room temperature thermoelectric Bi{sub 2}Te{sub 3}. We also discuss the impact of the band structure on deviations from Weidemann-Franz law as one tunes the chemical potential across the band gap.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping

Combining experimental spectroscopy and hybrid density functional theory calculations, we show that the incorporation of fluoride ions into a prototypical reducible oxide surface, namely, ceria(111), can induce a variety of nontrivial changes to the local electronic structure, beyond the expected increase in the number of Ce 3+ ions. Our resonant photoemission spectroscopy results reveal new states above, within, and below the valence band, which are unique to the presence of fluoride ions at the surface. With the help of hybrid density functional calculations, we show that the different states arise from fluoride ions in different atomic layers in the near surface region. In particular, we identify a structure in which a fluoride ion substitutes for an oxygen ion at the surface, with a second fluoride ion on top of a surface Ce 4+ ion giving rise to F 2p states which overlap the top of the O 2p band. The nature of this adsorbate F – –Ce 4+ resonant enhancement feature suggests that this bond is at least partially covalent. Here, our results demonstrate the versatility of anion doping as a potential means of tuning the valence band electronic structure of ceria.

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

Green’s function coupled cluster simulation of the near-valence ionizations of DNA-fragments

Accurate description of the ionization process in DNA is crucial to the understanding of the DNA damage under exposure to ionizing radiation and the exploration of the potential application of DNA strands in nanoelectronics. In this work, by employing our recently developed Green’s function coupled-cluster library on supercomputing facilities, we have studied the spectral functions of several guanine–cytosine (G–C) base pair structures ([G–C]n, n = 1–3) for the first time in a relatively broad near-valence regime ([−25.0, −5.0] eV) in the coupled-cluster with singles and doubles level. Our focus is to give a preliminary many-body coupled-cluster understanding and guideline of the vertical ionization energy (VIE), spectral profile, and ionization feature changes of these systems as the system size expands in this near-valence regime. The results show that, as the system size expands, even though the lowest VIEs keep decreasing, the changes of spectral function profile and the relative peak positions get unexpectedly smaller. Further analysis of the ionized states associated with the most intensive peak in the spectral functions reveals non-negligible |2h, 1p⟩’s in the ionized wave functions of the considered G–C base pair systems. The leading |2h, 1p⟩’s associated with the main ionizations from the cytosine part of the G–C base pairs feature a transition from the intra-base-pair cytosine π → π* excitation to the inter-base-pair electron excitation as the size of G–C base pairs expands, which also indicates the minimum quantum region in the many-body calculations of DNA systems.

Peng, Bo (ORCID:0000000242267294)↗
DOE OSTI2020

Excited state charge distribution and bond expansion of ferrous complexes observed with femtosecond valence-to-core x-ray emission spectroscopy

Valence-to-core x-ray emission spectroscopy (VtC XES) combines the sample flexibility and element specificity of hard x-rays with the chemical environment sensitivity of valence spectroscopy. Here, we extend this technique to study geometric and electronic structural changes induced by photoexcitation in the femtosecond time domain via laser-pump, x-ray probe experiments using an x-ray free electron laser. The results of time-resolved VtC XES on a series of ferrous complexes [Fe(CN) 2n (2, 2'-bipyridine) 3-n ] -2n+2 , n = 1, 2, 3, are presented. Comparisons of spectra obtained from ground state density functional theory calculations reveal signatures of excited state bond length and oxidation state changes. An oxidation state change associated with a metal-to-ligand charge transfer state with a lifetime of less than 100 fs is observed, as well as bond length changes associated with metal-centered excited states with lifetimes of 13 ps and 250 ps.

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

The role of high-order electron correlation effects in a model system for non-valence correlation-bound anions

The diffusion Monte Carlo (DMC), auxiliary field quantum Monte Carlo (AFQMC), and equation-of-motion coupled cluster (EOM-CC) methods are used to calculate the electron binding energy (EBE) of the non-valence anion state of a model (H2O)4 cluster. Two geometries are considered, one at which the anion is unbound and the other at which it is bound in the Hartree–Fock (HF) approximation. It is demonstrated that DMC calculations can recover from the use of a HF trial wave function that has collapsed onto a discretized continuum solution, although larger EBEs are obtained when using a trial wave function for the anion that provides a more realistic description of the charge distribution and, hence, of the nodal surface. For the geometry at which the cluster has a non-valence correlation-bound anion, both the inclusion of triples in the EOM-CC method and the inclusion of supplemental diffuse d functions in the basis set are important. DMC calculations with suitable trial wave functions give EBE values in good agreement with our best estimate EOM-CC result. AFQMC using a trial wave function for the anion with a realistic electron density gives a value of the EBE nearly identical to the EOM-CC result when using the same basis set. For the geometry at which the anion is bound in the HF approximation, the inclusion of triple excitations in the EOM-CC calculations is much less important. The best estimate EOM-CC EBE value is in good agreement with the results of DMC calculations with appropriate trial wave functions.

Upadhyay, Shiv (ORCID:0000000285010501)↗
DOE OSTI2021

Cation-size mismatch as a predictive descriptor for structural distortion, configurational disorder, and valence-band splitting in II-IV-N2 semiconductors

The II-IV-N2 class of heterovalent ternary nitrides has gained significant interest as alternatives to the III-nitrides for electronic and optoelectronic applications. In this study, we apply first-principles calculations based on density functional theory to systematically investigate the effects of structural distortions due to cation size mismatch on the configurational disorder of the cation sublattice and the valence band structure in this class of materials. We find that larger size mismatch between the group-II and the group-IV cations results in stronger lattice distortions from the ideal hexagonal ratio, which in turn inhibits the propensity of these materials toward octet-rule violating cation disorder. We also demonstrate that the formation energy of a single cation antisite pair, which is fast and simple to calculate, is a strong indicator of a material's propensity toward disorder. Furthermore, the breaking of in-plane symmetry leads to a splitting of the top three valence bands at Γ, which is also directly related to the magnitude of structural distortions. Our work demonstrates that the structural and functional properties of the II-IV-N2 materials can be finely tuned through controllable structural distortions that stem from the choice of cations.

Kute, Malhar (ORCID:0000000214364564)↗
DOE OSTI2023

Strongly coupled intermediate electronic states in one-color two-photon single valence ionization of O 2

Here, we present an experimental and theoretical energy- and angle-resolved investigation on the non-dissociative photoionization dynamics of near-resonant, one-color, two-photon, single valence ionization of neutral O 2 molecules. Using 9.3 eV femtosecond pulses produced via high harmonic generation and a 3-D momentum imaging spectrometer, we detect the photoelectrons and O$^{+}_{2}$ cations produced from one-color, two-photon ionization in coincidence. The measured and calculated photoelectron angular distributions show agreement, which indicates that a superposition of two intermediate electronic states is dominantly involved and that wavepacket motion on those near-resonantly populated intermediate states does not play a significant role in the measured two-photon ionization dynamics. Here, we find greater utility in the diabatic representation compared to the adiabatic representation, where invoking a single valence-character diabat is sufficient to describe the underlying two-photon ionization mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Electron and ion spectroscopy of azobenzene in the valence and core shells

Azobenzene is a prototype and a building block of a class of molecules of extreme technological interest as molecular photo-switches. We present a joint experimental and theoretical study of its response to irradiation with light across the UV to x-ray spectrum. The study of valence and inner shell photo-ionization and excitation processes combined with measurement of valence photoelectron-photoion coincidence and mass spectra across the core thresholds provides a detailed insight into the site- and state-selected photo-induced processes. Photo-ionization and excitation measurements are interpreted via the multi-configurational restricted active space self-consistent field method corrected by second order perturbation theory. Using static modeling, we demonstrate that the carbon and nitrogen K edges of azobenzene are suitable candidates for exploring its photoinduced dynamics thanks to the transient signals appearing in background-free regions of the NEXAFS and XPS.

Chemistry↗