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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 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Covalency of Trivalent Actinide Ions with Different Donor Ligands: Do Density Functional and Multiconfigurational Wavefunction Calculations Corroborate the Observed “Breaks”?

A comprehensive ab initio study of periodic actinide–ligand bonding trends for trivalent actinides is performed. Relativistic density functional theory (DFT) and complete active-space (CAS) self-consistent field wavefunction calculations are used to dissect the chemical bonding in the [AnCl 6 ] 3– , [An(CN) 6 ] 3– , [An(NCS) 6 ] 3– , [An(S 2 PMe 2 ) 3 ], [An(DPA) 3 ] 3– , and [An(HOPO)] – series of actinide (An = U–Es) complexes. Except for some differences for the early actinide complexes with DPA, bond orders and excess 5f-shell populations from donation bonding show qualitatively similar trends in 5f n active-space CAS vs DFT calculations. The influence of spin–orbit coupling on donation bonding is small for the tested systems. Along the actinide series, chemically soft vs chemically harder ligands exhibit clear differences in bonding trends. There are pronounced changes in the 5f populations when moving from Pu to Am or Cm, which correlate with previously noted “breaks” in chemical trends. As a result, bonding involving 5f becomes very weak beyond Cm/Bk. We propose that Cm(III) is a borderline case among the trivalent actinides that can be meaningfully considered to be involved in ground-state 5f covalent bonding.

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

A Practical Approach to Wave Function Propagation, Hopping Probabilities, and Time Steps in Surface Hopping Calculations

We compare several established approaches for propagating wave functions and calculating hopping probabilities within the fewest switches surface hopping (FSSH) algorithm for difficult cases with many electronic states and many trivial crossings. If only a single time step (Δt c ) is employed, we find that no published approach can accurately capture the dynamics correctly unless Δt c → 0 (which is not computationally feasible). If multiple time steps are employed, for a fixed classical time step (Δt c ), a robust scheme can be found for dynamically choosing quantum time steps (δt q1 and δt q2 ) and calculating hopping probabilities so that one can systematically reduce all errors and achieve maximally efficient accuracy; scattering calculations confirm that one can choose a fairly large classical time step. Furthermore, the robust scheme presented here uses both the “local diabatic” and adiabatic interpolation and thus borrows elements from both the Granucci/Persico and Meek/Levine algorithms. Our findings should be broadly applicable in the future.

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

A Synthetic Approach to β-Functionalized Naphtho[2,3]porphyrins

A concise synthetic method has been developed to access functionalized naphtho[2,3]porphyrins through combining two sequence reactions involving a Heck–electrocyclization–aromatization sequence and a Wittig–Knovenegal sequence. Using this method, mononaphtho[2,3]porphyrin (NP-1), opp-dinaphtho[2,3]porphyrin (NP-2), and push–pull naphtho[2,3]porphyrin (NP-3) have been prepared. These naphtho[2,3]porphyrins displayed interesting optical and electrochemical properties. As a result, excellent efficiencies of singlet oxygen generation were obtained for these naphtho[2,3]porphyrins.

Absorption↗
DOE OSTI2015

Chemical insight from density functional modeling of molecular adsorption: Tracking the bonding and diffusion of anthracene derivatives on Cu(111) with molecular orbitals

We present a method of analyzing the results of density functional modeling of molecular adsorption in terms of an analogue of molecular orbitals. This approach permits intuitive chemical insight into the adsorption process. Applied to a set of anthracene derivates (anthracene, 9,10-anthraquinone, 9,10-dithioanthracene, and 9,10-diselenonanthracene), we follow the electronic states of the molecules that are involved in the bonding process and correlate them to both the molecular adsorption geometry and the species’ diffusive behavior. We additionally provide computational code to easily repeat this analysis on any system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

A simple way to test for collinearity in spin symmetry broken wave functions: General theory and application to generalized Hartree Fock

We introduce a necessary and sufficient condition for an arbitrary wavefunction to be collinear, i.e., its spin is quantized along some axis. It may be used to obtain a cheap and simple computational procedure to test for collinearity in electronic structure theory calculations. We adapt the procedure for Generalized Hartree Fock (GHF), and use it to study two dissociation pathways in CO{sub 2}. For these dissociation processes, the GHF wave functions transform from low-spin Unrestricted Hartree Fock (UHF) type states to noncollinear GHF states and on to high-spin UHF type states, phenomena that are succinctly illustrated by the constituents of the collinearity test. This complements earlier GHF work on this molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Ion energy-angle distribution functions at the plasma-material interface in oblique magnetic fields

The ion energy-angle distribution (IEAD) at the wall of a magnetized plasma is of fundamental importance for the determination of the material processes occurring at the plasma-material interface, comprising secondary emissions and material sputtering. Here, we present a numerical characterization of the IEAD at the wall of a weakly collisional magnetized plasma with the magnetic field inclined at an arbitrary angle with respect to the wall. The analysis has been done using two different techniques: (1) a fluid-Monte Carlo method, and (2) particle-in-cell simulations, the former offering a fast but approximate method for the determination of the IEADs, the latter giving a computationally intensive but self-consistent treatment of the plasma behavior from the quasi-neutral region to the material boundary. The two models predict similar IEADs, whose similarities and differences are discussed. Data are presented for magnetic fields inclined at angles from normal to grazing incidence (0°–85°). We show the scaling factors of the average and peak ion energy and trends of the pitch angle at the wall as a function of the magnetic angle, for use in the correlation of fluid plasma models to material models.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

In-operando synchronous time-multiplexed O K-edge x-ray absorption spectromicroscopy of functioning tantalum oxide memristors

Memristors are receiving keen interest because of their potential varied applications and promising large-scale information storage capabilities. Tantalum oxide is a memristive material that has shown promise for high-performance nonvolatile computer memory. The microphysics has been elusive because of the small scale and subtle physical changes that accompany conductance switching. In this study, we probed the atomic composition, local chemistry, and electronic structure of functioning tantalum oxide memristors through spatially mapped O K-edge x-ray absorption. We developed a time-multiplexed spectromicroscopy technique to enhance the weak and possibly localized oxide modifications with spatial and spectral resolutions of <30 nm and 70 meV, respectively. During the initial stages of conductance switching of a micrometer sized crosspoint device, the spectral changes were uniform within the spatial resolution of our technique. When the device was further driven with millions of high voltage-pulse cycles, we observed lateral motion and separation of ∼100 nm-scale agglomerates of both oxygen interstitials and vacancies. We also demonstrate a unique capability of this technique by identifying the relaxation behavior in the material during electrical stimuli by identifying electric field driven changes with varying pulse widths. In addition, we show that changes to the material can be localized to a spatial region by modifying its topography or uniformity, as against spatially uniform changes observed here during memristive switching. The goal of this report is to introduce the capability of time-multiplexed x-ray spectromicroscopy in studying weak-signal transitions in inhomogeneous media through the example of the operation and temporal evolution of a memristor.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Spin orientations of the spin-half Ir{sup 4+} ions in Sr{sub 3}NiIrO{sub 6}, Sr{sub 2}IrO{sub 4}, and Na{sub 2}IrO{sub 3}: Density functional, perturbation theory, and Madelung potential analyses

The spins of the low-spin Ir{sup 4+} (S = 1/2, d{sup 5}) ions at the octahedral sites of the oxides Sr{sub 3}NiIrO{sub 6}, Sr{sub 2}IrO{sub 4}, and Na{sub 2}IrO{sub 3} exhibit preferred orientations with respect to their IrO{sub 6} octahedra. We evaluated the magnetic anisotropies of these S = 1/2 ions on the basis of density functional theory (DFT) calculations including spin-orbit coupling (SOC), and probed their origin by performing perturbation theory analyses with SOC as perturbation within the LS coupling scheme. The observed spin orientations of Sr{sub 3}NiIrO{sub 6} and Sr{sub 2}IrO{sub 4} are correctly predicted by DFT calculations, and are accounted for by the perturbation theory analysis. As for the spin orientation of Na{sub 2}IrO{sub 3}, both experimental studies and DFT calculations have not been unequivocal. Our analysis reveals that the Ir{sup 4+} spin orientation of Na{sub 2}IrO{sub 3} should have nonzero components along the c- and a-axis directions. The spin orientations determined by DFT calculations are sensitive to the accuracy of the crystal structures employed, which is explained by perturbation theory analyses when interactions between adjacent Ir{sup 4+} ions are taken into consideration. There are indications implying that the 5d electrons of Na{sub 2}IrO{sub 3} are less strongly localized compared with those of Sr{sub 3}NiIrO{sub 6} and Sr{sub 2}IrO{sub 4}. This implication was confirmed by showing that the Madelung potentials of the Ir{sup 4+} ions are less negative in Na{sub 2}IrO{sub 3} than in Sr{sub 3}NiIrO{sub 6} and Sr{sub 2}IrO{sub 4}. Most transition-metal S = 1/2 ions do have magnetic anisotropies because the SOC induces interactions among their crystal-field split d-states, and the associated mixing of the states modifies only the orbital parts of the states. This finding cannot be mimicked by a spin Hamiltonian because this model Hamiltonian lacks the orbital degree of freedom, thereby leading to the spin-half syndrome. The spin-orbital entanglement for the 5d spin-half ions Ir{sup 4+} is not as strong as has been assumed.

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

Sequential double excitations from linear-response time-dependent density functional theory

Traditional UV/vis and X-ray spectroscopies focus mainly on the study of excitations starting exclusively from electronic ground states. However there are many experiments where transitions from excited states, both absorption and emission, are probed. In this work we develop a formalism based on linear-response time-dependent density functional theory to investigate spectroscopic properties of excited states. We apply our model to study the excited-state absorption of a diplatinum(II) complex under X-rays, and transient vis/UV absorption of pyrene and azobenzene.

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

Understanding the pseudocapacitance of RuO 2 from joint density functional theory

Pseudocapacitors have been experimentally studied for many years in electric energy storage. However, first principles understanding of the pseudocapacitive behavior is still not satisfactory due to the complexity involved in modeling electrochemistry. In this paper, we applied joint density functional theory (JDFT) to simulate the pseudocapacitive behavior of RuO 2 , a prototypical material, in a model electrolyte. Additionally, we obtained from JDFT a capacitive curve which showed a redox peak position comparable to that in the experimental cyclic voltammetry (CV) curve. We found that the experimental turning point from double-layer to pseudocapacitive charge storage at low scan rates could be explained by the hydrogen adsorption at low coverage. As the electrode voltage becomes more negative, H coverage increases and causes the surface-structure change, leading to bended –OH bonds at the on-top oxygen atoms and large capacitance. This H coverage-dependent capacitance can explain the high pseudocapacitance of hydrous RuO 2 . In conclusion, our work here provides a first principles understanding of the pseudocapacitance for RuO 2 in particular and for transition-metal oxides in general.

double layer capacitance↗
DOE OSTI2018

Density-functional theory for systems with noncollinear spin: Orbital-dependent exchange-correlation functionals and their application to the Hubbard dimer

Here, a class of orbital-dependent exchange-correlation potentials for applications in noncollinear spin-density-functional theory is developed. Starting from the optimized effective potential formalism for the exact exchange potential—generalized to the noncollinear case—correlation effects are added via a self-consistent procedure inspired by the Singwi-Tosi-Land-Sjölander method. The orbital-dependent exchange-correlation potentials are applied to the Hubbard dimer in uniform and noncollinear magnetic fields and compared to exact diagonalization and to the Bethe-ansatz local spin-density approximation. The Singwi-Tosi-Land-Sjölander method gives the overall best performance for total energies, densities, and magnetizations, particularly in the weakly to moderately correlated regime.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗