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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy) 2 ] 2+

Theoretical predictions show that depending on the populations of the Fe 3dxy, 3dxz, and 3dyz orbitals two possible quintet states can exist for the high-spin state of the photoswitchable model system [Fe(terpy)2]2+. The differences in the structure and molecular properties of these 5B2 and 5E quintets are very small and pose a substantial challenge for experiments to resolve them. Yet for a better understanding of the physics of this system, which can lead to the design of novel molecules with enhanced photoswitching performance, it is vital to determine which high-spin state is reached in the transitions that follow the light excitation. The quintet state can be prepared with a short laser pulse and can be studied with cutting-edge time-resolved X-ray techniques. Here we report on the application of an extended set of X-ray spectroscopy and scattering techniques applied to investigate the quintet state of [Fe(terpy)2]2+ 80 ps after light excitation. High-quality X-ray absorption, nonresonant emission, and resonant emission spectra as well as X-ray diffuse scattering data clearly reflect the formation of the high-spin state of the [Fe(terpy)2]2+ molecule; moreover, extended X-ray absorption fine structure spectroscopy resolves the Fe-ligand bond-length variations with unprecedented bondlength accuracy in time-resolved experiments. With ab initio calculations we determine why, in contrast to most related systems, one configurational mode is insufficient for the description of the low-spin (LS)-high-spin (HS) transition. We identify the electronic structure origin of the differences between the two possible quintet modes, and finally, we unambiguously identify the formed quintet state as 5E, in agreement with our theoretical expectations.

Vankó, György↗
DOE OSTI2015

Communication: State-to-state dynamics of the Cl + H{sub 2}O → HCl + OH reaction: Energy flow into reaction coordinate and transition-state control of product energy disposal

Quantum state-to-state dynamics of a prototypical four-atom reaction, namely, Cl + H{sub 2}O → HCl + OH, is investigated for the first time in full dimensionality using a transition-state wave packet method. The state-to-state reactivity and its dependence on the reactant internal excitations are analyzed and found to share many similarities both energetically and dynamically with the H + H{sub 2}O → H{sub 2} + OH reaction. The strong enhancement of reactivity by the H{sub 2}O stretching vibrational excitations in both reactions is attributed to the favorable energy flow into the reaction coordinate near the transition state. On the other hand, the insensitivity of the product state distributions with regard to reactant internal excitation stems apparently from the transition-state control of product energy disposal.

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

A Medium-/Low-Voltage Joint State Estimator Through Linear Uncertainty Propagation

Traditionally, distribution system state estimations (DSSE) are challenged by the lack of measurements at both primary and secondary sides of the system. The widely available cable television (CATV) voltage sensors installed in low-voltage (LV) networks bring opportunities to achieve higher quality DSSE covering a broader area of the distribution network. This study proposes a medium-/low-voltage (MV/LV) joint distribution system state estimation approach using the untapped CATV measurements. It aims at addressing the need for system situational awareness at the grid edge while improving the estimation accuracy at both the primary and secondary sides compared to its disjointed counterpart. Linearized measurement functions and boundary condition uncertainty propagation rules are derived to ensure the computational efficiency and accuracy of the joint state estimator. Numerical experiments are conducted on an IEEE test feeder to demonstrate the efficacy of the proposed method and the value of CATV measurements.

joint state estimation↗
DOE OSTI2015

Atomic solid state energy scale: Universality and periodic trends in oxidation state

The atomic solid state energy (SSE) scale originates from a plot of the electron affinity (EA) and ionization potential (IP) versus band gap (E{sub G}). SSE is estimated for a given atom by assessing an average EA (for a cation) or an average IP (for an anion) for binary inorganic compounds having that specific atom as a constituent. Physically, SSE is an experimentally-derived average frontier orbital energy referenced to the vacuum level. In its original formulation, 69 binary closed-shell inorganic semiconductors and insulators were employed as a database, providing SSE estimates for 40 elements. In this contribution, EA and IP versus E{sub G} are plotted for an additional 92 compounds, thus yielding SSE estimates for a total of 64 elements from the s-, p-, d-, and f-blocks of the periodic table. Additionally, SSE is refined to account for its dependence on oxidation state. Although most cations within the SSE database are found to occur in a single oxidation state, data are available for nine d-block transition metals and one p-block main group metal in more than one oxidation state. SSE is deeper in energy for a higher cation oxidation state. Two p-block main group non-metals within the SSE database are found to exist in both positive and negative oxidation states so that they can function as a cation or anion. SSEs for most cations are positioned above −4.5 eV with respect to the vacuum level, and SSEs for all anions are positioned below. Hence, the energy −4.5 eV, equal to the hydrogen donor/acceptor ionization energy ε(+/−) or equivalently the standard hydrogen electrode energy, is considered to be an absolute energy reference for chemical bonding in the solid state. - Highlights: • Atomic solid-state energies are estimated for 64 elements from experimental data. • The relationship between atomic SSEs and oxidation state is assessed. • Cations are positioned above and absolute energy of −4.5 eV and anions below.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Methods to Calculate Electronic Excited-State Dynamics for Molecules on Large Metal Clusters with Many States: Ensuring Fast Overlap Calculations and a Robust Choice of Phase

Here, we present an efficient set of methods for propagating excited-state dynamics involving a large number of configuration interaction singles (CIS) or Tamm-Dancoff approximation (TDA) single-reference excited states. Specifically, (i) following Head-Gordon et al., we implement an exact evaluation of the overlap of singly-excited CIS/TDA electronic states at different nuclear geometries using a biorthogonal basis and (ii) we employ a unified protocol for choosing the correct phase for each adiabat at each geometry. For many-electron systems, the combination of these techniques significantly reduces the computational cost of integrating the electronic Schrodinger equation and imposes minimal overhead on top of the underlying electronic structure calculation. As a demonstration, we calculate the electronic excited-state dynamics for a hydrogen molecule scattering off a silver metal cluster, focusing on high-lying excited states, where many electrons can be excited collectively and crossings are plentiful. Interestingly, we find that the high-lying, plasmon-like collective excitation spectrum changes with nuclear dynamics, highlighting the need to simulate non-adiabatic nuclear dynamics and plasmonic excitations simultaneously. In the future, the combination of methods presented here should help theorists build a mechanistic understanding of plasmon-assisted charge transfer and excitation energy relaxation processes near a nanoparticle or metal surface.

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

Quantum mechanical calculations of state-to-state cross sections and rate constants for the F + DCl → Cl + DF reaction

We present accurate state-to-state quantum wave packet calculations of integral cross sections and rate constants for the title reaction. Calculations are carried out on the best available ground 1{sup 2}A′ global adiabatic potential energy surface of Deskevich et al. [J. Chem. Phys. 124, 224303 (2006)]. Converged state-to-state reaction cross sections have been calculated for collision energies up to 0.5 eV and different initial rotational and vibrational excitations, DCl(v = 0, j = 0 − 1; v = 1, j = 0). Also, initial-state resolved rate constants of the title reaction have been calculated in a temperature range of 100-400 K. It is found that the initial rotational excitation of the DCl molecule does not enhance reactivity, in contract to the reaction with the isotopologue HCl in which initial rotational excitation produces an important enhancement. These differences between the isotopologue reactions are analyzed in detail and attributed to the presence of resonances for HCl(v = 0, j), absent in the case of DCl(v = 0, j). For vibrational excited DCl(v = 1, j), however, the reaction cross section increases noticeably, what is also explained by another resonance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Consolidation of composite cathodes with NCM and sulfide solid-state electrolytes by hot pressing for all-solid-state Li metal batteries

In this study, hot pressing was evaluated as a method of cell fabrication to increase the energy density of next-generation all-solid-state batteries with NCM active material and sulfide solid-state electrolyte. Hot pressing involves consolidating glassy sulfide electrolyte by the application of pressure at a temperature above the electrolyte’s glass transition temperature. Typically, cell stacks are formed at room temperature and retain 15–30% porosity that limits cell energy density. On the other hand, the porosity of hot-pressed cell stacks is reduced to less than 10%. The electrochemical function of hot-pressed cathode composites was assessed as a function of active material and solid-state electrolyte compositions. Specifically, LiNi 0.85 Co 0.10 Mn 0.05 O 2 and LiNi 0.6 Co 0.2 Mn 0.2 O 2 were studied in combination with either glassy Li 7 P 3 S 11 , glassy Li 3 PS 4 , or β-Li 3 PS 4 solid-state electrolytes. Cathode composites composed of LiNi 0.6 Co 0.2 Mn 0.2 O 2 and Li 3 PS 4 maintained the best function after hot pressing at 200 °C and 370 MPa for 10 min. It was found that LiNi 0.6 Co 0.2 Mn 0.2 O 2 ’s resistance to microcracking and the inherent stability of Li 3 PS 4 ’s fully de-networked local structure are critical to maintain good electrochemical function after hot pressing. Furthermore, the results of this study show that hot pressing reduces porosity in the cathode composite and confirms the feasibility of cathode support of consolidated, reinforced glass separators.

25 ENERGY STORAGE↗
DOE OSTI2015

Isobar analog states (IAS), double isobar analog states (DIAS), configuration states (CS), and double configuration states (DCS) in halo nuclei. Halo isomers

It has been shown that IAS, DIAS, CS, and DCS can simultaneously have n-n, n-p, and p-p halo components in their wave functions. Differences in halo structure of the excited and ground states can result in the formation of isomers (halo-isomers). Both the Borromean and tango halo types can be observed for n-p configurations of atomic nuclei. The structure of the ground and excited states with different isospin quantum number in halo like nuclei is discussed. B(Mλ) and B(Eλ) for γ-transitions in {sup 6,7,8}Li, {sup 8,9,10}Be, {sup 8,10,11}B, {sup 10,11,12,13,14}C, {sup 13,14,15,16,17}N, {sup 15,16,17,19}O, and {sup 17}F are analyzed. Special attention is given to nuclei whose ground state does not exhibit halo structure but the excited state may have one.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2015

State-to-state reaction dynamics of {sup 18}O+{sup 32}O{sub 2} studied by a time-dependent quantum wavepacket method

The title isotope exchange reaction was studied by converged time-dependent wave packet calculations, where an efficient 4th order split operator was applied to propagate the initial wave packet. State-to-state differential and integral cross sections up to the collision energy of 0.35 eV were obtained with {sup 32}O{sub 2} in the hypothetical j{sub 0} = 0 state. It is discovered that the differential cross sections are largely forward biased in the studied collision energy range, due to the fact that there is a considerable part of the reaction occurring with large impact parameter and short lifetime relative to the rotational period of the intermediate complex. The oscillations of the forward scattering amplitude as a function of collision energy, which result from coherent contribution of adjacent resonances, may be a sensitive probe for examining the quality of the underlying potential energy surface. A good agreement between the theoretical and recent experimental integral and differential cross sections at collision energy of 7.3 kcal/mol is obtained. However, the theoretical results predict slightly too much forward scattering and colder rotational distributions than the experimental observations at collision energy of 5.7 kcal/mol.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

Excited states via coupled cluster theory without equation-of-motion methods: Seeking higher roots with application to doubly excited states and double core hole states

Here, in this work, we revisited the idea of using the coupled-cluster (CC) ground state formalism to target excited states. Our main focus was targeting doubly excited states and double core hole states. Typical equation-of-motion (EOM) approaches for obtaining these states struggle without higher-order excitations than doubles. We showed that by using a non-Aufbau determinant optimized via the maximum overlap method, the CC ground state solver can target higher energy states. Furthermore, just with singles and doubles (i.e., CCSD), we demonstrated that the accuracy of ΔCCSD and ΔCCSD(T) (triples) far surpasses that of EOM-CCSD for doubly excited states. The accuracy of ΔCCSD(T) is nearly exact for doubly excited states considered in this work. For double core hole states, we used an improved ansatz for greater numerical stability by freezing core hole orbitals. The improved methods, core valence separation (CVS)-ΔCCSD and CVS-ΔCCSD(T), were applied to the calculation of the double ionization potential of small molecules. Even without relativistic corrections, we observed qualitatively accurate results with CVS-ΔCCSD and CVS-ΔCCSD(T). Remaining challenges in ΔCC include the description of open-shell singlet excited states with the single-reference CC ground state formalism as well as excited states with genuine multireference character. The tools and intuition developed in this work may serve as a stepping stone toward directly targeting arbitrary excited states using ground state CC methods.

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

Involvement of a low-lying Rydberg state in the ultrafast relaxation dynamics of ethylene

We present a measurement of the time-resolved photoelectron kinetic energy spectrum of ethylene using 156 nm and 260 nm laser pulses. The 156 nm pulse first excites ethylene to the {sup 1}B{sub 1u} (ππ{sup ∗}) electronic state where 260 nm light photoionizes the system to probe the relaxation dynamics with sub-30 fs resolution. Recent ab initio calculations by Mori et al. [J. Phys. Chem. A 116, 2808-2818 (2012)] have predicted an ultrafast population transfer from the initially excited state to a low-lying Rydberg state during the relaxation of photoexcited ethylene. The measured photoelectron kinetic energy spectrum reveals wave packet motion on the valence state and shows indications that the low-lying π3s Rydberg state is indeed transiently populated via internal conversion following excitation to the ππ{sup ∗} state, supporting the theoretical predictions.

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

Behavior of the maximum likelihood in quantum state tomography

Quantum state tomography on a d-dimensional system demands resources that grow rapidly with d. They may be reduced by using model selection to tailor the number of parameters in the model (i.e., the size of the density matrix). Most model selection methods typically rely on a test statistic and a null theory that describes its behavior when two models are equally good. Here, we consider the loglikelihood ratio. Because of the positivity constraint ρ ≥ 0, quantum state space does not generally satisfy local asymptotic normality (LAN), meaning the classical null theory for the loglikelihood ratio (the Wilks theorem) should not be used. Thus, understanding and quantifying how positivity affects the null behavior of this test statistic is necessary for its use in model selection for state tomography. We define a new generalization of LAN, metric-projected LAN, show that quantum state space satisfies it, and derive a replacement for the Wilks theorem. In addition to enabling reliable model selection, our results shed more light on the qualitative effects of the positivity constraint on state tomography.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

F-state quenching with CH{sub 4} for buffer-gas cooled {sup 171}Y b{sup +} frequency standard

We report that methane, CH{sub 4}, can be used as an efficient F-state quenching gas for trapped ytterbium ions. The quenching rate coefficient is measured to be (2.8 ± 0.3) × 10{sup 6} s{sup −1} Torr{sup −1}. For applications that use microwave hyperfine transitions of the ground-state {sup 171}Y b ions, the CH{sub 4} induced frequency shift coefficient and the decoherence rate coefficient are measured as δν/ν = (−3.6 ± 0.1) × 10{sup −6} Torr{sup −1} and 1/T{sub 2} = (1.5 ± 0.2) × 10{sup 5} s{sup −1} Torr{sup −1}. In our buffer-gas cooled {sup 171}Y b{sup +} microwave clock system, we find that only ≤10{sup −8} Torr of CH{sub 4} is required under normal operating conditions to efficiently clear the F-state and maintain ≥85% of trapped ions in the ground state with insignificant pressure shift and collisional decoherence of the clock resonance.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2015

Non-equilibrium oxidation states of zirconium during early stages of metal oxidation

The chemical state of Zr during the initial, self-limiting stage of oxidation on single crystal zirconium (0001), with oxide thickness on the order of 1 nm, was probed by synchrotron x-ray photoelectron spectroscopy. Quantitative analysis of the Zr 3d spectrum by the spectrum reconstruction method demonstrated the formation of Zr 1+ , Zr 2+ , and Zr 3+ as non-equilibrium oxidation states, in addition to Zr 4+ in the stoichiometric ZrO 2 . This finding resolves the long-debated question of whether it is possible to form any valence states between Zr 0 and Zr 4+ at the metal-oxide interface. As a result, the presence of local strong electric fields and the minimization of interfacial energy are assessed and demonstrated as mechanisms that can drive the formation of these non-equilibrium valence states of Zr.

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

Calculation of state-to-state differential and integral cross sections for atom-diatom reactions with transition-state wave packets

A recently proposed transition-state wave packet method [R. Welsch, F. Huarte-Larrañaga, and U. Manthe, J. Chem. Phys. 136, 064117 (2012)] provides an efficient and intuitive framework to study reactive quantum scattering at the state-to-state level. It propagates a few transition-state wave packets, defined by the eigenfunctions of the low-rank thermal flux operator located near the transition state, into the asymptotic regions of the reactant and product arrangement channels separately using the corresponding Jacobi coordinates. The entire S-matrix can then be assembled from the corresponding flux-flux cross-correlation functions for all arrangement channels. Since the transition-state wave packets can be defined in a relatively small region, its transformation into either the reactant or product Jacobi coordinates is accurate and efficient. Furthermore, the grid/basis for the propagation, including the maximum helicity quantum number K, is much smaller than that required in conventional wave packet treatments of state-to-state reactive scattering. This approach is implemented for atom-diatom reactions using a time-dependent wave packet method and applied to the H + D{sub 2} reaction with all partial waves. Excellent agreement with benchmark integral and differential cross sections is achieved.

97 MATHEMATICS AND COMPUTING↗