The Electronic Structure of Lutein 2 Is Optimized for Light Harvesting in Plants
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
SEARCH · Search NASA
Results for “electronic structures”
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Layer-Dependent Interaction Effects in the Electronic Structure of Twisted Bilayer Graphene Devices
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Two-Dimensional Electronic Spectroscopies for Probing Electronic Structure and Charge Transfer: Applications to Photosystem II
Photosystem II (PSII) is the only known natural enzyme that uses solar energy to split water, making the elucidation of its design principles critical for our fundamental understanding of photosynthesis and for our ability to mimic PSII’s remarkable properties. This report discusses progress towards addressing key open questions about the PSII RC. It describes new spectroscopic methods that were developed to answer these questions, and summarizes the outcomes of applying these methods to study the PSII RC. Using 2D electronic spectroscopy and 2D electronic Stark spectroscopy, models for the PSII RC were tested and refined. Work is ongoing to use the collected data to elucidate the charge separation mechanism in the PSII RC. Coherent dynamics were also observed in the PSII RC for the first time. Through extensive characterization and modeling we have assigned these coherences as vibronic in nature, and believe that they reflect resonances between key vibrational pigment modes and electronic energy gaps that may facilitate charge separation. Work is ongoing to definitively test the functional relevance of electronic-vibrational resonances.
14 SOLAR ENERGY↗
Elucidating the Role of Dimensionality on the Electronic Structure of the Van der Waals Antiferromagnet NiPS 3
Abstract The sustained interest in investigating magnetism in the 2D limit of insulating antiferromagnets is driven by the possibilities of discovering, or engineering, novel magnetic phases through layer stacking. However, due to the difficulty of directly measuring magnetic interactions in 2D antiferromagnets, it is not yet understood how intra layer magnetic interactions in insulating , strongly correlated, materials can be modified through layer proximity. Herein, the impact of reduced dimensionality in the model van der Waals antiferromagnet NiPS 3 is explored by measuring electronic excitations in exfoliated samples using Resonant Inelastic X‐ray Scattering (RIXS). The resulting spectra shows systematic broadening of NiS 6 multiplet excitations with decreasing layer count from bulk down to three atomic layers (3L). It is shown that these trends originate from a decrease in transition metal‐ligand and ligand–ligand hopping integrals, and by charge‐transfer energy evolving from Δ = 0.83 eV in the bulk to 0.37 eV in 3L NiPS 3 . Relevant intralayer magnetic exchange integrals computed from the electronic parameters exhibit a decrease in the average interaction strength with thickness. This study underscores the influence of inter layer electronic interactions on intra layer ones in insulating magnets, indicating that magnetic Hamiltonians in few‐layer insulating magnets can greatly deviate from their bulk counterparts.
36 MATERIALS SCIENCE↗
Nonrigid band shift and nonmonotonic electronic structure changes upon doping in the normal state of the pnictide high-temperature superconductor Ba ( F e 1 - x C o x ) 2 A s 2
Here, we report systematic angle-resolved photoemission (ARPES) experiments using different photon polarizations and experimental geometries and find that the doping evolution of the normal state of Ba(Fe 1–x Co x ) 2 As 2 deviates significantly from the predictions of a rigid band model. The data reveal a nonmonotonic dependence upon doping of key quantities such as band filling, bandwidth of the electron pocket, and quasiparticle coherence. Our analysis suggests that the observed phenomenology and the inapplicability of the rigid band model in Co-doped Ba122 are due to electronic correlations, and not to the either the strength of the impurity potential, or self-energy effects due to impurity scattering. Our findings indicate that the effects of doping in pnictides are much more complicated than currently believed. More generally, they indicate that a deep understanding of the evolution of the electronic properties of the normal state, which requires an understanding of the doping process, remains elusive even for the 122 iron-pnictides, which are viewed as the least correlated of the high-T C unconventional superconductors.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
The Electronic Structure of Zirconium and Hafnium Monochalcogenides
High-level ab initio CCSD(T) and spin–orbit icMRCI+Q calculations were used to predict potential energy curves (PECs) for the lowest-lying states of ZrO, ZrS, HfO, and HfS. The prediction of the ground state is basis set dependent at the icMRCI+Q level for ZrO and ZrS due to the small singlet–triplet splitting between the lowest 1 Σ + and 3 Δ states. CCSD(T) with a spin orbit correction predicted the 1 Σ + ground state in agreement with experiment. New all-electron basis sets were developed for Hf to improve the results over those predicted by use of effective core potentials (ECPs) that subsume the 4f electrons into the definition of the core. The use of the new DK-4f basis sets rather than ECPs became more important for HfO and HfS where there is a lack of a good core–valence separation. icMRCI+Q, CCSD(T), and DFT calculations for the spectroscopic parameters of ZrO, ZrS, HfO, and HfS were benchmarked with available experimental data. Bond dissociation energies (BDEs) of these four systems were calculated at the Feller–Peterson–Dixon (FPD) level to be 762.1 (ZrO), 543.5 (ZrS), 803.8 (HfO), and 575.1 kJ/mol (HfS), in excellent agreement with experiment. The HfS BDE was remeasured using the R3PI method, providing an updated experimental measurement of D 0 (HfS) = 5.978 ± 0.002 eV = 576.8 ± 0.2 kJ/mol. This experimental value, combined with experimental measurements of the ionization energies of Hf and HfS, gives the cationic BDE of D 0 (Hf + -S) = 5.124 ± 0.002 eV = 494.4 ± 0.2 kJ/mol.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Understanding How Isotopes Affect Charge Transfer in P3HT/PCBM: A Quantum Trajectory-Electronic Structure Study with Nonlinear Quantum Corrections
The experimentally observed effect of selective deuterium substitution on the open circuit voltage for a blend of poly(3-hexylthiophene)(P3HT) and [6,6]-phenyl-C 61 - butyric acid methyl ester (PCBM) (Nat. Commun. 5:3180, 2014) is explored using a 221-atom model of a polymer-wrapped PCBM molecule. We describe the protonic and deuteronic wavefunctions for the H/D isotopologues of the hexyl side chains within a Quantum Trajectory/Electronic Structure approach where the dynamics is performed with newly developed nonlinear corrections to the quantum forces, necessary to describe the nuclear wavefunctions; the classical forces are generated with a Density Functional Tight Binding method. We used the resulting protonic and deuteronic time-dependent wavefunctions to assess the effects of isotopic substitution (deuteration) on the energy gaps relevant to the charge transfer for the donor and acceptor electronic states. Furthermore, while the isotope effect on the electronic energy levels is found negligible, the quantum-induced fluctuations of the energy gap between the charge transfer and charge separated states due to nuclear wavefunctions may account for experimental trends by promoting charge transfer in P3HT/PCBM and increasing charge recombination on the donor in the deuterium substituted P3HT/PCBM.
36 MATERIALS SCIENCE↗
Dissecting Electronic-Structural Transitions in the Nitrogenase MoFe Protein P-Cluster during Reduction
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Electronic structure of compressively strained thin film La$_2$PrNi$_2$O$_7$
The discovery of superconductivity in the bulk nickelates under high pressure is a major advance in physics. The recent observation of superconductivity at ambient pressure in compressively strained bilayer nickelate thin films has now enabled direct characterization of the superconducting phase through angle resolved photoemission spectroscopy (ARPES). Here we present an in-situ ARPES study of compressively strained La$_2$PrNi$_2$O$_7$ films grown by oxide molecular beam epitaxy, and the ozone treated counterparts with an onset T$_c$ of 40 K, supplemented with results from pulsed laser deposition films with similar T$_c$. We resolve a systematic strain-driven electronic band shift with respect to that of bulk crystals, in qualitative agreement with density functional theory (DFT) calculations. However, the strongly renormalized flat 3$d_{z2}$ band shifts a factor of 5-10 smaller than anticipated by DFT. Furthermore, it stays ~70 meV below the Fermi level, contradicting the expectation that superconductivity results from the high density of states of this band at the Fermi level. We also observed a non-trivial k$_z$ dispersion of the cuprate-like 3$d_{x2-y2}$ band. Combined with results from both X-ray diffraction and DFT, we suggest that the strained films are under ~5 GPa effective pressure, considerably larger than the naïve expectation from the DFT relaxed structure. Finally, the ~70 meV energy position is intriguingly close to the collective mode coupling more prominently seen in thin films, in the energy range of both oxygen related phonons and the maximum of the spin excitation spectrum.
FOS: Physical sciences↗
Trans-Influence in Dinuclear Pt(III) Complexes: Electronic Structure, σ-Donation, and Pt–Pt Spin–Spin Coupling
This study investigates the trans influence in dinuclear platinum(III) complexes using a combined approach of ab initio molecular dynamics and natural localized molecular orbital (NLMO) analysis. Focusing on pivalamidate-bridged Pt III complexes with axial ligands of varying σ-donation strength, it is quantified how ligand−metal interactions propagate through the Pt−Pt bond, and how they affect bond polarization, axial water coordination, and 1 J PtPt spin−spin coupling constants. NLMO analysis reveals quantitatively that strong σ-donating ligands polarize the Pt−Pt bond, shifting the electron density toward the opposite platinum center. The polarization mechanism is identified as the primary reason for the observed reduction of 1 J PtPt , because the bond polarization diminishes the transmission of the nuclear magnetic spin-induced electron spin density through the Pt−Pt bond. Additionally, the destabilization of axial water coordination at the opposite Pt site can be rationalized through a polarizationinduced Pt IV − Pt II -like mixed-valence character.
Ab initio molecular dynamics↗
Extracting the electronic structure of light elements in bulk materials through a Compton scattering method in the readily accessible hard x-ray regime
Here, our Compton profile measurements of Ti and TiH 2 using readily available hard X-ray radiation at 27.5 keV, detected by both a Hitachi Vortex silicon-drift detector and a high-resolution superconducting transition-edge sensor array, are found to be in excellent accord with state-of-the-art density functional theory based calculations. The spherically averaged difference between the Compton profiles of TiH 2 and Ti is well described by an inverted parabola, supporting an itinerant behavior of the electron gas screening the protons in the Ti matrix. Our experimental approach, validated by two different detectors, extends the applicability of Compton scattering technique to the readily accessible hard x-ray regime (below 30 keV). Our study suggests possibilities for experiments at low-flux bending magnet synchrotron beamlines and paves the way for the development of tabletop Compton experiments with x-ray tubes.
36 MATERIALS SCIENCE↗
Electronic Structure and Bonding of US, SUO, and US 2
Anion photoelectron spectra of US – and US 2 – were recorded using the third (355 nm) and fourth (266 nm) harmonics of an Nd:YAG laser, which yielded vertical detachment energies (VDEs) of 1.71 and 2.02 eV, respectively. The experimental results are supported by extensive relativistic ab initio calculations, primarily at the coupled cluster level of theory, with systematic sequences of correlation consistent basis sets. Calculations include the closely related SUO and SUO – molecules, as well as the oxide congeners UO/UO – and UO 2 /UO 2 – which are well-known experimentally and provide benchmark systems for the sulfide calculations. Adiabatic electron detachment energies (ADEs) are computed for UO – , UO 2 – , US – , SUO – , and US 2 – using the Feller–Peterson–Dixon (FPD) composite approach. Additionally, ADEs are determined for UO – and US – using a spinor-based coupled cluster approach where spin–orbit coupling is included at the orbital level. VDEs are derived from the ab initio results from Franck–Condon simulations of the photoelectron spectra.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Electronic Structure and Optical Properties of Designed Photo-Efficient Indoline-Based Dye-Sensitizers with D–A–π–A Framework
Seven D–A–π–A-based indoline (IND) dyes that were designed via quantitative-structure–property relationship modeling have been comprehensively investigated using computational approaches to evaluate their prospect of application in future dye-sensitized solar cells (DSSCs). An array of optoelectronic properties of the isolated dye and dyes adsorbed on a TiO 2 cluster that simulates the semiconductor were explored by density functional theory (DFT) and time-dependent DFT methods. Light absorption spectra, vertical dipole moment, shift of the conduction band of semiconductor, excited state lifetime, driving force of electron injection, photostability of the excited state, and exciton binding energy were computed. Our study showed that the presence of an internal acceptor such as pyrido[3,4-b]pyrazine (pyrazine) would influence greater the open circuit voltage (VOC), compared to the benzothiadiazole moiety. Considering the balance between the VOC and J SC (short circuit current) along with the all calculated characteristics, the IND3, IND5, and IND10 are the most suited among the designed dyes to be used as potential candidates for the photo-efficient DSSCs. Finally, the present study provides the results of rational molecular design followed by exploration of photophysical properties to be used as a valuable reference for the synthesis of photo-efficient dyes for DSSCs.
14 SOLAR ENERGY↗
Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure
Separations of f-block elements are a critical aspect of nuclear waste processing. Redox-based separations offer promise, but challenges remain in stabilizing and differentiating actinides in high oxidation states. The investigation of new ligand types that provide thermodynamic stabilization to high-valent actinides is essential for expanding their fundamental chemistry and to elaborate new separation techniques and storage methods. We report herein the preparation and characterization of Th and U complexes of the pyridyl-hydroxylamine ligand, N-tert-butyl-N-(pyridin-2-yl)hydroxylamine (pyNO–). Electrochemical studies performed on the homoleptic complexes [M(pyNO) 4 ] (M = Th, U) revealed significant stabilization of the U complex upon one-electron oxidation. The salt [U(pyNO) 4 ] + was isolated by chemical oxidation of [U(pyNO) 4 ]; spectroscopic and computational data support assignment as a U V cation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Determining the Electronic Structure of Paramagnetic Intermediates in membrane proteins: A high-resolution 2D 1H hyperfine sublevel correlation study of the redox-active tyrosines of photosystem II
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Structural, electronic, and magnetic properties of CoFeVGe-based compounds: Experiment and theory
We have carried out a combined theoretical and experimental investigation of both stoichiometric and nonstoichiometric CoFeVGe alloys. In particular, we have investigated CoFeVGe, Co 1.25 Fe 0.75 VGe, Co 0.75 Fe 1.25 VGe, and CoFe 0.75 VGe bulk alloys. Our first principles calculations suggest that all four alloys show ferromagnetic order, where CoFeVGe, Co 1.25 Fe 0.75 VGe, and Co 0.75 Fe 1.25 VGe are highly spin polarized with spin polarization values of over 80%. However, the spin polarization value of CoFe 0.75 VGe is only about 60%. We have synthesized all four samples using arc melting and high-vacuum annealing at 600 °C for 48 hours. The room temperature x-ray diffraction of these samples exhibits a cubic crystal structure with disorder. All the samples show single magnetic transitions at their Curie temperatures, where the Curie temperature and high field (3T) magnetization are 288 K and 42 emu/g; 305 K and 1.5 emu/g; 238 K and 39 emu/g; and 306 K and 35 emu/g for CoFeVGe, Co 1.25 Fe 0.75 VGe, Co 0.75 Fe 1.25 VGe, and CoFe 0.75 VGe, respectively.
36 MATERIALS SCIENCE↗
Electronic Structure Correspondence of Singlet-Triplet Scale Separation in Strained Sr2RuO4
At a temperature of roughly 1 K, Sr 2 RuO 4 undergoes a transition from a normal Fermi liquid to a superconducting phase. Even while the former is relatively simple and well understood, the superconducting state has not even been understood after 25 years of study. More recently, it has been found that critical temperatures can be enhanced by the application of uniaxial strain, up to a critical strain, after which it falls off. In this work, we take an “instability” approach and seek divergences in susceptibilities. This provides an unbiased way to distinguish tendencies to competing ground states. We show that in the unstrained compound, the singlet and triplet instabilities of the normal Fermi liquid phase are closely spaced. Under uniaxial strain, electrons residing on all orbitals contributing to the Fermiology become more coherent, while the electrons of the Ru-dxy character become heavier, and the electrons of the Ru d x z , y z characters become lighter. In the process, Im χ(q,ω) increases rapidly around q = ( 0.3 , 0.3 , 0 ) 2 π / a and q = ( 0.5 , 0.25 , 0 ) 2 π / a , while it gets suppressed at all other commensurate vectors, in particular at q = 0, which is essential for spin-triplet superconductivity. We observe that the magnetic anisotropy under strain drops smoothly, which is concomitant with the increment in singlet instability. Thus, the triplet superconducting instability remains the lagging instability of the system, and the singlet instability enhances under strain, leading to a large energy-scale separation between these competing instabilities. However, since this happens even without spin-orbit coupling, we believe it is primarily the enhancement in the spin fluctuation glue around quasi-anti-ferromagnetic vectors that drives the Cooper pairing instead of the magnetic anisotropy. At large strain, an instability to a spin density wave overtakes the superconducting one. The analysis relies on a high-fidelity, ab initio description of the one-particle properties and two-particle susceptibilities, based on the quasiparticle self-consistent GW approximation augmented by dynamical mean field theory. This approach is described and its high fidelity confirmed by comparing to observed one- and two-particle properties.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗