Theoretical evidence for multiple one-electron 3d bonding in a first row transition metal dimer - The 5 Sigma u -state of Sc2
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Walch, S. P.↗
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The Role of Spin–Orbit Coupling in the Linear Absorption Spectrum and Intersystem Crossing Rate Coefficients of Ruthenium Polypyridyl Dyes
The successful use of molecular dyes for solar energy conversion requires efficient charge injection, which in turn requires the formation of states with sufficiently long lifetimes (e.g., triplets). The molecular structure elements that confer this property can be found empirically, however computational predictions using ab initio electronic structure methods are invaluable to identify structure-property relations for dye sensitizers. The primary challenge for simulations to elucidate the electronic and nuclear origins of these properties is a spin-orbit interaction which drives transitions between electronic states. Here, in this work, we present a computational analysis of the spin-orbit corrected linear absorption cross sections and intersystem crossing rate coefficients for a derivative set of phosphonated tris(2,2'-bipyridine)ruthenium(2+) dye molecules. After sampling the ground state vibrational distributions, the predicted linear absorption cross sections indicate that the mixture between singlet and triplet states plays a crucial role in defining the line shape of the metal-to-ligand charge transfer bands in these derivatives. Additionally, an analysis of the intersystem crossing rate coefficients suggests that transitions from the singlet into the triplet manifolds are ultrafast with rate coefficients on the order of 10 13 s -1 for each dye molecule.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Gapless Dirac surface states in the antiferromagnetic topological insulator MnBi 2 Te 4
We used angle-resolved photoemission spectroscopy (ARPES) and density functional theory calculations to study the electronic properties of MnBi 2 Te 4 , a material that was predicted to be an intrinsic antiferromagnetic (AFM) topological insulator. In striking contrast to earlier literature showing a full gap opening between two surface band manifolds on the (0001) surface, we observed a gapless Dirac surface state with a Dirac point sitting at E B = -280 meV . Furthermore, our ARPES data revealed the existence of a second Dirac cone sitting closer to the Fermi level. Surprisingly, these surface states remain intact across the AFM transition. The presence of gapless Dirac states in this material may be caused by different ordering at the surface from the bulk or weaker magnetic coupling between the bulk and surface. Whereas the surface Dirac cones seem to be remarkably insensitive to the AFM ordering most likely due to weak coupling to magnetism, we did observe a splitting of the bulk band accompanying the AFM transition. Finally, with a moderately high ordering temperature and interesting gapless Dirac surface states, MnBi 2 Te 4 provides a unique platform for studying the interplay between magnetic ordering and topology.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Nonradiative relaxation in tunable solid state laser crystals
The characteristics of nonradiative transitions between the 4T2 and 2E excited states of trivalent-chromium-ion-activated ruby (containing 0.04 percent Cr2O3 by weight) and alexandrite (containing 0.4 at. percent chromium ion) laser crystals were studied using the technique described by Gayen et al. (1985). In this technique, a 527-nm pulse excites the 4T2 band of the Cr(3+), and the subsequent population kinetics among excited states is monitored by an IR picosecond probe pulse as a function of pump-probe delay. In ruby, a resolution-limited sharp rise in the excited state population was followed by a long-lifetime decay, leading to an upper limit of 7 ps for the 4T2-state nonradiative lifetime. In alexandrite, a longer rise time was followed by a multicomponent decay. A theoretical model is proposed for explaining the induced absorption and the transition dynamics observed in these crystals.
Gayen, S. K.↗
A Computational Study of RNA Tetraloop Thermodynamics, Including Misfolded States
An important characteristic of RNA folding is the adoption of alternative configurations of similar stability, often referred to as misfolded configurations. These configurations are considered to compete with correctly folded configurations, although their rigorous thermodynamic and structural characterization remains elusive. Tetraloop motifs found in large ribozymes are ideal systems for an atomistically detailed computational quantification of folding free energy landscapes and the structural characterization of their constituent free energy basins, including nonnative states. In this work, we studied a group of closely related 10-mer tetraloops using a combined parallel tempering and metadynamics technique that allows a reliable sampling of the free energy landscapes, requiring only knowledge that the stem folds into a canonical A-RNA configuration. Here we isolated and analyzed unfolded, folded, and misfolded populations that correspond to different free energy basins. We identified a distinct misfolded state that has a stability very close to that of the correctly folded state. This misfolded state contains a predominant population that shares the same structural features across all tetraloops studied here and lacks the noncanonical A-G base pair in its loop portion. Further analysis performed with biased trajectories showed that although this competitive misfolded state is not an essential intermediate, it is visited in most of the transitions from unfolded to correctly folded states. Moreover, the tetraloops can transition from this misfolded state to the correctly folded state without requiring extensive unfolding.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Hybrid Turbine Electric Vehicle
Hybrid electric power trains may revolutionize today's ground passenger vehicles by significantly improving fuel economy and decreasing emissions. The NASA Lewis Research Center is working with industry, universities, and Government to develop and demonstrate a hybrid electric vehicle. Our partners include Bowling Green State University, the Cleveland Regional Transit Authority, Lincoln Electric Motor Division, the State of Ohio's Department of Development, and Teledyne Ryan Aeronautical. The vehicle will be a heavy class urban transit bus offering double the fuel economy of today's buses and emissions that are reduced to 1/10th of the Environmental Protection Agency's standards. At the heart of the vehicle's drive train is a natural-gas-fueled engine. Initially, a small automotive engine will be tested as a baseline. This will be followed by the introduction of an advanced gas turbine developed from an aircraft jet engine. The engine turns a high-speed generator, producing electricity. Power from both the generator and an onboard energy storage system is then provided to a variable-speed electric motor attached to the rear drive axle. An intelligent power-control system determines the most efficient operation of the engine and energy storage system.
Viterna, Larry A.↗
The nature of the DX state in Ge-doped AlGaN
Electrical conductivity in high Al-content AlGaN has been severely limited, presumably due to a DX transition forming an acceptor state and subsequent self-compensation, which imposed an upper limit on the achievable free carrier concentration. To elucidate this idea, this paper examines Ge doping as a function of Al-content in AlGaN and finds a different behavior: for Al compositions below 40%, Ge behaved as a shallow donor with an ionization energy below 20 meV, while for Al compositions above 40%, above DX transition, it emerged as a deep donor. The ionization energy of this deep state increased with increasing Al content and reached 150 meV for 60% AlGaN. Around the DX transition, a continuous change from the shallow to deep donor was observed. In contrast to the density functional theory predictions, acceptor-type states corresponding to a DX-type transition were not observed. This finding may have profound technological consequences for the development of AlGaN- and AlN-based devices as it offers a feasible pathway to high n-conductivity in these compounds.
Physics↗
Effects of Plasma on Physical Properties of Water: Nanocrystalline-to-Amorphous Phase Transition and Improving Produce Washing
Washing fresh produce using Plasma-activated water recently became a promising eco-friendly alternative to using chemical additives such as Chlorine. We discuss the produce-washing experiments that illustrate that addition of plasma to washing water is a multi-faced phenomena. Not only it increases the sterilization ability of water by killing pathogens, but it also has improved washibility: the ability to remove pathogens from the cleaning surface. We propose an explanation of these features based on the recently discoveries that many physical and chemical properties of water change their temperature dependence between about 35 and 60 degrees Celsius. In particular, heat conductance, light absorption, and surface tension all change their temperature dependence. These drastic changes were associated with water gradually changing its mesoscopic structure: while at the higher temperatures water is a uniform media (amorphous state), at the temperatures below transition it consists of many nano-to-micro-scale clusters (crystalline state). This transition is similar to the second order phase transition. In the present paper we propose that treating water with non-thermal plasma (adding plasma-created active compounds) can lower the temperature of the transition and thus cause a significant change in such physical quantities as surface tension, viscosity, freezing rate, and wettability and washability.
He, Jinjie↗
Elucidating and Mitigating High-Voltage Degradation Cascades in Cobalt-Free LiNiO 2 Lithium-Ion Battery Cathodes
LiNiO 2 (LNO) is a promising cathode material for next-generation Li-ion batteries due to its exceptionally high capacity and cobalt-free composition that enables more sustainable and ethical large-scale manufacturing. However, its poor cycle life at high operating voltages over 4.1 V impedes its practical use, thus motivating efforts to elucidate and mitigate LiNiO 2 degradation mechanisms at high states of charge. Here, a multiscale exploration of high-voltage degradation cascades associated with oxygen stacking chemistry in cobalt-free LiNiO 2 , is presented. In this work, lattice oxygen loss is found to play a critical role in the local O3–O1 stacking transition at high states of charge, which subsequently leads to Ni-ion migration and irreversible stacking faults during cycling. This undesirable atomic-scale structural evolution accelerates microscale electrochemical creep, cracking, and even bending of layers, ultimately resulting in macroscopic mechanical degradation of LNO particles. By employing a graphene-based hermetic surface coating, oxygen loss is attenuated in LNO at high states of charge, which suppresses the initiation of the degradation cascade and thus substantially improves the high-voltage capacity retention of LNO. Overall, this study provides mechanistic insight into the high-voltage degradation of LNO, which will inform ongoing efforts to employ cobalt-free cathodes in Li-ion battery technology.
25 ENERGY STORAGE↗
Tuning Shinkarev’s Bicycle: Separating the Parallel Cycles of Photosystem II Using Empirical Wavelet Transform
The oxygen-evolving complex (OEC) of Photosystem II (PSII) catalyzes light-driven water oxidation, a process necessary to sustain Earth’s atmospheric oxygen. Oxygen yields measured during single-turnover flash sequences exhibit period-four oscillations, which form the basis of the Joliot–Kok (S-state) model. However, when the oscillations of other processes contribute to the measured oxygen yield, fitting methods can conflate these signals and distort estimates of inefficiencies and initial S-state populations. To address this, we applied the empirical wavelet transform (EWT) as a model-independent method to separate overlapping oscillators and capture damping dynamics that are not well represented in Fourier analysis. We tested this framework on polarographic flash-oxygen traces from both our Synechocystis sp. PCC 6803 thylakoid membrane preparations and archival datasets on Chlorella and isolated chloroplasts. EWT consistently resolves the expected period-four component alongside a distinct binary oscillation. Simulations suggest that fitting this isolated period-four signal recovers VZAD parameters more accurately than analysis of raw traces, yielding different estimates for S-state distributions and transition probabilities. Notably, this binary oscillation aligns closely with semiquinone dynamics predicted solely from period-four fit parameters. These findings indicate that EWT can effectively distinguish complex signals in oxygen evolution, offering a framework potentially applicable to other spectroscopic probes of the S-state cycle.
Ferrari, Nicholas [Louisiana State Univ., Baton Ro↗
Single-Crystallization of O3-Type Layered Oxide Cathode for Na-Ion Battery
The development of high-energy-density Na-ion batteries places significant demands on single-crystal layered oxide cathodes, especially for further high-voltage, solid-state battery scenarios. In the O3-type structure, due to the original sluggish Na ion diffusion kinetics (approximately 1 order of magnitude lower than that of Li-ion), and further hindrance against diffusion kinetics caused by single-crystal architecture, these inherent defects lead to the decline in the electrochemical performance. Herein, we demonstrated that the single crystallization of O3-type NaNi 1/3 Fe 1/3 Mn 1/3 O 2 cathode (d 50 = 5.04 μm) aggravates surface-to-bulk phase inhomogeneity distribution, which is attributed to the uneven Na ions extraction. Moreover, the Na-depletion of the surface/shell region not only aggravates Na ion diffusion resistance but also leads to a higher valence state of transition-metal elements (e.g., Ni/Fe) near the surface of the single-crystal particle, which further compromises the cathode-electrolyte interface stability. Furthermore, not limited to revealing the challenges, tuning the particle size and moderating quasi-single-crystal strategies have been proven to effectively mitigate the negative uneven distributions of Na ions, phases, and valence/oxidative states, resulting in efficient modification for single crystallization of Na-layered oxide cathodes.
36 MATERIALS SCIENCE↗
The rotational spectrum of nitric acid - The first five vibrational states
The details of work on the nu(8) vibrational state, which arise from the NO2 out-of-plane vibration, are reported. For this state, over 210 transitions have been measured in the millimeter and submillimeter spectral region and analyzed with Watson's A-reduced centrifugal distortion Hamiltonian. Also included in this work is a comparison of all these spectra and an overview of the millimeter and submillimeter spectra associated with these states. Although at the high sensitivity available in laboratory experiments, many additional lines are observable, all arise from vibrational states whose populations are more than 100 times lower than the ground state. The most prominent of these are due to the states which give rise to the perturbed 2 nu(9) and nu(5) bands near 11 microns. These results provide a significant data base for both atmospheric remote sensing experiments and spectral analyses of data in other spectral regions, especially the IR.
Crownover, Richard L.↗
Debonding-on-demand reversible adhesives via heat or light with competitive adhesion strength to conventional epoxy adhesives
Stimuli responsive debonding-on-demand (DoD) reversible adhesives are of great interest for the circular economy. However, the reversible adhesives developed so far often lack competitive adhesion strength in a bonding state. In this work, reversible epoxy adhesives based on Diels–Alder (DA) chemistry were developed and exhibited a competitive adhesion strength (e.g., 12 – 16 MPa of a lap shear strength) to commercial non-reversible epoxy adhesives. The reversible epoxy formulation showed superior thermal stability up to 110°C, and transition to a debonding state in the order of 0.1 MPa at 140°C, consequently, an on/off-type debonding behavior. The transition to a debonding state was attributed to crosslinking density control (e.g., decrease by 33% – 49%) through the reversible DA chemistry and the proximity to the glass transition. Next, for debonding by light stimulus, photothermal refractory plasmonic titanium nitride (TiN) nanoparticles were incorporated in the reversible epoxy, which can generate the required heat for debonding upon exposure to visible light. Photothermal debonding allows for precise debonding at target areas and tunable adhesion strength by controlling the exposure area and light intensity. The DA adhesive formulations containing 0.5 wt.% TiN nanoparticles presented a debonding state with zero adhesion under light exposure with intensity of 1670 mW/cm 2 (inducing 140°C). Even after three cycles of reattachment, the DA adhesive formulations retained 96% of the pristine sample’s adhesion strength measured at 110°C. Therefore, the DA adhesives are attractive candidates as reversible DoD systems applicable in higher temperatures.
42 ENGINEERING↗
First-principles study of the structures and redox mechanisms of Ni-rich lithium nickel manganese cobalt oxides
To reduce the cobalt (Co) content in lithium-ion batteries, Ni-rich (high-Ni) lithium nickel manganese cobalt oxides (NMC) are pursued as one of the next-generation cathode materials. However, there is still debate on the crystal and electronic structures of the baseline, LiNiO 2 . Density Functional Theory (DFT) calculations were performed to provide a theoretical understanding of Ni-rich NMC. First, it was found that the commonly used $R\bar{3}m$ structure for LiNiO 2 is metallic, contrary to the experimentally reported mix-conducting behavior. Among the four different space groups, $R\bar{3}m$, C2/m, P2 1 /c, and P2/c, P2/c with charge disproportionation of Ni 2+ and Ni 4+ is the most energetically stable and semiconducting structure of LiNiO 2 . Therefore, the atomic structures of representative Ni-rich NMC were built by partially replacing Ni with Co or Mn in the P2/c LiNiO 2 to form Li x Ni y Mn z Co 1-y-z O 2 . In the fully lithiated (x=1.0) high Ni content NMC (y>0.5), the oxidation state of all Mn ions becomes 4+, while Co ions still maintain 3+, and part of the Ni ions become 3+ to compensate for the charge. Upon delithiation, the local environment shows more variation of the charge states on the transition metal (TM) ions. The average oxidation on each TM follows a sequence of losing electrons that starts from Ni 2+ to Ni 3+ , then oxidizing Ni 3+ and Co 3+ , while Mn 4+ remains electrochemically inactive till x=0. Finally, a general relationship for the oxidation state change in each TM as a function of x is derived and shows agreement with both modeling and experimental data.
25 ENERGY STORAGE↗
Closed-form solution of decomposable stochastic models
Markov and semi-Markov processes are increasingly being used in the modeling of complex reconfigurable systems (fault tolerant computers). The estimation of the reliability (or some measure of performance) of the system reduces to solving the process for its state probabilities. Such a model may exhibit numerous states and complicated transition distributions, contributing to an expensive and numerically delicate solution procedure. Thus, when a system exhibits a decomposition property, either structurally (autonomous subsystems), or behaviorally (component failure versus reconfiguration), it is desirable to exploit this decomposition in the reliability calculation. In interesting cases there can be failure states which arise from non-failure states of the subsystems. Equations are presented which allow the computation of failure probabilities of the total (combined) model without requiring a complete solution of the combined model. This material is presented within the context of closed-form functional representation of probabilities as utilized in the Symbolic Hierarchical Automated Reliability and Performance Evaluator (SHARPE) tool. The techniques adopted enable one to compute such probability functions for a much wider class of systems at a reduced computational cost. Several examples show how the method is used, especially in enhancing the versatility of the SHARPE tool.
Sjogren, Jon A.↗
Reversible disorder-order transitions in atomic crystal nucleation
Nucleation in atomic crystallization remains poorly understood, despite advances in classical nucleation theory. The nucleation process has been described to involve a nonclassical mechanism that includes a spontaneous transition from disordered to crystalline states, but a detailed understanding of dynamics requires further investigation. In situ electron microscopy of heterogeneous nucleation of individual gold nanocrystals with millisecond temporal resolution shows that the early stage of atomic crystallization proceeds through dynamic structural fluctuations between disordered and crystalline states, rather than through a single irreversible transition. Our experimental and theoretical analyses support the idea that structural fluctuations originate from size-dependent thermodynamic stability of the two states in atomic clusters. These findings, based on dynamics in a real atomic system, reshape and improve our understanding of nucleation mechanisms in atomic crystallization.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
Tunable Magnetic Exchange between Rare-Earth Metal 5d and Iron 3d States: A Case Study of the Multiple Magnetic Transitions in Gd 6 FeBi 2 and the Solid Solutions Dy 6– x Gd x FeBi 2 (1 ≤ x ≤ 5) with Curie Temperatures in the Range 120–350 K
In this paper, the room-temperature magnet Gd 6 FeBi 2 was comprehensively characterized by means of temperature-dependent single-crystal X-ray diffraction, magnetization measurements, and experimental electron density and electronic structure computations. This work explores the electron-spin effects of Fe on this structure and suggests that Gd6FeBi2 shows structural features and exchange interactions, which are clearly distinguishable from other analogues, including the solid solutions Dy 6–x Gd x FeBi 2 (0 ≤ x ≤ 5). The unique traits of Gd 6 FeBi 2 and its derivatives encompass abnormal variations of lattice parameters with the temperature, as well as the presence of multiple magnetic transitions of complex nature. Based on the comprehensive analyses, it can be suggested that the unique magnetic response in this material is the result from tunable Fe spin states, which are coupled with strong Gd 5d–Fe 3d interactions, which differ from other members of this large, structural family. In the ground state, according to density functional theory calculations, the Fe atom carries two net electrons, whose spins are coupled in an antiparallel fashion to the spins of the Gd electrons. Near the Curie temperature, the Fe net moment is reduced intermittently, coupled with a multiple of magnetic transitions. The magnetic correlations are manifested in unexpected variations of the lattice parameters as a function of temperature, suggesting spin–lattice interactions. Furthermore, this study emphasizes the important role of Gd 5d electrons in tuning Fe 3d-based magnetic contribution, which enables better understanding on the spin coupling in other related compounds and sheds light on the development of new magnetic and spintronic compounds.
36 MATERIALS SCIENCE↗
Electrical Manipulation of Topological Phases in a Quantum Anomalous Hall Insulator
Quantum anomalous Hall phases arising from the inverted band topology in magnetically doped topological insulators have emerged as an important subject of research for quantization at zero magnetic fields. Though necessary for practical implementation, sophisticated electrical control of molecular beam epitaxy (MBE)-grown quantum anomalous Hall matter have been stymied by growth and fabrication challenges. Here, in this study, a novel procedure is demonstrated, employing a combination of thin-film deposition and 2D material stacking techniques, to create dual-gated devices of the MBE-grown quantum anomalous Hall insulator, Cr-doped (Bi,Sb) 2 Te 3 . In these devices, orthogonal control over the field-induced charge density and the electric displacement field is demonstrated. A thorough examination of material responses to tuning along each control axis is presented, realizing magnetic property control along the former and a novel capability to manipulate the surface exchange gap along the latter. Through electrically addressing the exchange gap, the capabilities to either strengthen the quantum anomalous Hall state or suppress it entirely and drive a topological phase transition to a trivial state are demonstrated. The experimental result is explained using first principle theoretical calculations, and establishes a practical route for in situ control of quantum anomalous Hall states and topology.
36 MATERIALS SCIENCE↗