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Materials Data on LiV(SiO3)2 by Materials Project

LiVSi2O6 is Esseneite structured and crystallizes in the monoclinic Cc space group. The structure is three-dimensional. Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.07–2.53 Å. V3+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six SiO4 tetrahedra and edges with two equivalent VO6 octahedra. There are a spread of V–O bond distances ranging from 1.96–2.12 Å. There are two inequivalent Si4+ sites. In the first Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share corners with three equivalent VO6 octahedra and corners with two equivalent SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 34–59°. There is one shorter (1.62 Å) and three longer (1.65 Å) Si–O bond length. In the second Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share corners with three equivalent VO6 octahedra and corners with two equivalent SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 33–59°. There is one shorter (1.61 Å) and three longer (1.65 Å) Si–O bond length. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded to one Li1+, two equivalent V3+, and one Si4+ atom to form a mixture of distorted edge and corner-sharing OLiV2Si trigonal pyramids. In the second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Li1+ and two equivalent Si4+ atoms. In the third O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Li1+ and two equivalent Si4+ atoms. In the fourth O2- site, O2- is bonded in a distorted T-shaped geometry to one Li1+, one V3+, and one Si4+ atom. In the fifth O2- site, O2- is bonded to one Li1+, two equivalent V3+, and one Si4+ atom to form a mixture of distorted edge and corner-sharing OLiV2Si trigonal pyramids. In the sixth O2- site, O2- is bonded in a distorted T-shaped geometry to one Li1+, one V3+, and one Si4+ atom.

36 MATERIALS SCIENCE↗

Hund’s flat band in a frustrated spinel oxide

Electronic flat bands associated with quenched kinetic energy and heavy electron mass have attracted great interest for promoting strong electronic correlations and emergent phenomena such as high-temperature charge fractionalization and superconductivity. Intense experimental and theoretical research has been devoted to establishing the rich nontrivial metallic and heavy fermion phases intertwined with such localized electronic states. Here, in this study, we investigate the transition metal oxide spinel LiV 2 O 4 , an enigmatic heavy fermion compound lacking localized f orbital states. We use angle-resolved photoemission spectroscopy and dynamical mean-field theory to reveal a kind of correlation-induced flat band with suppressed interatomic electron hopping arising from intra-atomic Hund’s coupling. The appearance of heavy quasiparticles is ascribed to a proximate orbital-selective Mott state characterized by fluctuating local moments as evidenced by complementary magnetotransport measurements. The spectroscopic fingerprints of long-lived quasiparticles and their disappearance with increasing temperature further support the emergence of a high-temperature “bad” metal state observed in transport data. This work resolves a long-standing puzzle on the origin of heavy fermion behavior and unconventional transport in LiV 2 O 4 . Simultaneously, it opens a path to achieving flat bands through electronic interactions in d-orbital systems with geometrical frustration, potentially enabling the realization of exotic phases of matter such as the fractionalized Fermi liquids.

36 MATERIALS SCIENCE↗

Unconventional polaronic ground state in superconducting LiTi 2 O 4

Geometrically frustrated lattices can display a range of correlated phenomena, ranging from spin frustration and charge order to dispersionless flat bands due to quantum interference. One particularly compelling family of such materials is the half-valence spinel LiB 2 O 4 materials. On the B-site frustrated pyrochlore sublattice, the interplay of correlated metallic behavior and charge frustration leads to a superconducting state in LiTi 2 O 4 and heavy fermion behavior in LiV 2 O 4 . To date, however, LiTi 2 O 4 has primarily been understood as a conventional BCS superconductor despite a lattice structure that could host more exotic ground states. Here, we present a multimodal investigation of LiTi 2 O 4 , combining ARPES, RIXS, proximate magnetic probes, and ab-initio many-body theoretical calculations. Our data reveals a novel mobile polaronic ground state with spectroscopic signatures that underlie co-dominant electron-phonon coupling and electron-electron correlations also found in the lightly doped cuprates. The cooperation between the two interaction scales distinguishes LiTi 2 O 4 from other superconducting titanates, suggesting an unconventional origin to superconductivity in LiTi 2 O 4 . Our work deepens our understanding of the rare interplay of electron-electron correlations and electron-phonon coupling in unconventional superconducting systems. In particular, our work identifies the geometrically frustrated, mixed-valence spinel family as an under-explored platform for discovering unconventional, correlated ground states.

36 MATERIALS SCIENCE↗

Tuning the Solvation Structure in Aqueous Zinc Batteries to Maximize Zn-Ion Intercalation and Optimize Dendrite-Free Zinc Plating

Aqueous zinc batteries are recognized to suffer from H + /Zn 2+ coinsertion in the cathode, but few approaches have been reported to suppress deleterious H + intercalation. We realize this goal by tuning the solvation structure, using LiV 2 (PO 4 ) 3 (LVP) as a model cathode. Phase conversion of LVP induced by H + intercalation is observed in 4 m Zn(OTf) 2 , whereas dominant Zn 2+ insertion is confirmed in a ZnCl 2 water-in-salt electrolyte (WiSE). This disparity is ascribed to the complete absence of free water and a strong Zn 2+ –H 2 O interaction in the latter that interrupts the H 2 O hydrogen bonding network, thus suppressing H + intercalation. On the basis of this strategy, a novel PEG-based hybrid electrolyte is designed to replace the corrosive ZnCl2 WiSE. This system exhibits an optimized Zn 2+ solvation sheath with a similar low free water content, showing not only much better suppression of H + intercalation but also highly reversible Zn plating/stripping with a CE of ~99.7% over 150 cycles.

25 ENERGY STORAGE↗

Impact of simultaneous activities on frequency fluctuations — comprehensive analyses based on the real measurement data from FNET/GridEye

Simultaneous human activities such as the Super Bowl game would cause certain impacts on frequency fluctuations in power systems. With the help of FNET/GridEye measurements, this work aims to give comprehensive analyses on the frequency fluctuations during Super Bowl LIV held on Feb. 2, 2020, so as to better understand several phenomena caused by simultaneous activities and help system operation and control. First, recent developments of FNET/GridEye are introduced briefly. Second, the frequency fluctuations of Eastern Interconnection (EI), western electricity coordinating council (WECC), and electric reliability council of Texas (ERCOT) power systems during Super Bowl LIV are analyzed. Third, frequency fluctuations of Super Bowl Sunday and ordinary Sundays in 2020 are compared. Finally, the differences of frequency fluctuations among different years during the Super Bowl and their change trend are also given. Furthermore, several possible explanations including the simultaneity of electricity consumption at the beginning of commercial breaks and the halftime show, the increasing usage of the Internet, and the increasing size of TV screens are illustrated in detail in this work.

24 POWER TRANSMISSION AND DISTRIBUTION↗

A disordered rock salt anode for fast-charging lithium-ion batteries

Rechargeable lithium-ion batteries with high energy density that can be safely charged and discharged at high rates are desirable for electrified transportation and other applications. However, the sub-optimal intercalation potentials of current anodes result in a trade-off between energy density, power and safety. In this paper we report that disordered rock salt Li 3+ x V 2 O 5 can be used as a fast-charging anode that can reversibly cycle two lithium ions at an average voltage of about 0.6 volts versus a Li/Li + reference electrode. The increased potential compared to graphite reduces the likelihood of lithium metal plating if proper charging controls are used, alleviating a major safety concern (short-circuiting related to Li dendrite growth). In addition, a lithium-ion battery with a disordered rock salt Li 3 V 2 O 5 anode yields a cell voltage much higher than does a battery using a commercial fast-charging lithium titanate anode or other intercalation anode candidates (Li 3 VO 4 and LiV 0.5 Ti 0.5 S 2 ). Further, disordered rock salt Li 3 V 2 O 5 can perform over 1,000 charge–discharge cycles with negligible capacity decay and exhibits exceptional rate capability, delivering over 40 per cent of its capacity in 20 seconds. We attribute the low voltage and high rate capability of disordered rock salt Li 3 V 2 O 5 to a redistributive lithium intercalation mechanism with low energy barriers revealed via ab initio calculations. This low-potential, high-rate intercalation reaction can be used to identify other metal oxide anodes for fast-charging, long-life lithium-ion batteries.

25 ENERGY STORAGE↗

Systems-level investigation of aqueous batteries for understanding the benefit of water-in-salt electrolyte by synchrotron nanoimaging

Water-in-salt (WIS) electrolytes provide a promising path toward aqueous battery systems with enlarged operating voltage windows for better safety and environmental sustainability. In this work, a new electrode couple, LiV 3 O 8 -LiMn 2 O 4 , for aqueous Li-ion batteries is investigated to understand the mechanism by which the WIS electrolyte improves the cycling stability at an extended voltage window. Operando synchrotron transmission x-ray microscopy on the LiMn 2 O 4 cathode reveals that the WIS electrolyte suppresses the mechanical damage to the electrode network and dissolution of the electrode particles, in addition to delaying the water decomposition process. Because the viscosity of WIS is notably higher, the reaction heterogeneity of the electrodes is quantified with x-ray absorption spectroscopic imaging, visualizing the kinetic limitations of the WIS electrolyte. This work furthers the mechanistic understanding of electrode–WIS electrolyte interactions and paves the way to explore the strategy to mitigate their possible kinetic limitations in three-dimensional architectures.

36 MATERIALS SCIENCE↗

High Energy Astrophysics Tests of Lorentz Invariance and Quantum Gravity Models

High energy astrophysics observations provide the best possibilities to detect a very small violation of Lorentz invariance such as may be related to the structure of space-time near the Planck scale of approximately 10(exp -35)m. I will discuss the possible signatures of Lorentz invariance violation (LIV) that can be manifested by observing of the spectra, polarization, and timing of gamma-rays from active galactic nuclei and y-ray bursts. Other sensitive tests are provided by observations of the spectra of ultrahigh energy cosmic rays and neutrinos. Using the latest data from the Pierre Auger Observatory one can already derive an upper limit of 4.5 x 10(exp -23) on the fraction of LIV at a Lorentz factor of approximately 2 x 10(exp 11). This result has fundamental implications for quantum gravity models. I will also discuss the possibilities of using more sensitive space-based detection techniques to improve searches for LIV in the future.

Stecker, F. W.↗

High Energy Astrophysics Tests of Lorentz Invariance and Quantum Gravity Models

High energy astrophysics observations provide the best possibilities to detect a very small violation of Lorentz invariance such as may be related to the structure of space-time near the Planck scale of approx.10(exp -35) m. I will discuss the possible signatures of Lorentz invariance violation (LIV) that can be manifested by observing of the spectra, polarization, and timing of gamma-rays from active galactic nuclei and gamma-ray bursts. Other sensitive tests are provided by observations of the spectra of ultrahigh energy cosmic rays and neutrinos. Using the latest data from the Pierre Auger Observatory one can already derive an upper limit of 4.5 x 10(exp -23) on the fraction of LIV at a Lorentz factor of approx. 2 x 10(exp 11). This result has fundamental implications for quantum gravity models. I will also discuss the possibilities of using more sensitive space-based detection techniques to improve searches for LIV in the future. I will also discuss how the LIV formalism casts doubt on the OPERA superluminal neutrino claim.

Stecker, Floyd W.↗

Investigation of Ga 2 O 3 as a new transparent conductive oxide for photovoltaics applications

This small innovation project intended to leverage recent activity and advances in ultrawide-bandgap oxide power electronics toward the investigation of Ga 2 O 3 as a transparent conductive oxide (TCO) for use in photovoltaics (PV). Ga 2 O 3 ’s theoretical advantage over incumbent TCOs is its very large bandgap of 4.8 eV, ensuring optical transparency of photons with λ ≥ 260 nm, effectively the full terrestrial solar spectrum. At the time of proposal writing, literature on Ga 2 O 3 as a TCO/optical material was relatively sparse — what little existed was focused on for UV sensors and/or emitters, with none related to PV. As such, this project was intended to help determine the potential of Ga 2 O 3 as a PV-oriented TCO by investigating its deposition using tools common to the PV and electronics industries — atomic layer deposition (ALD) and RF sputtering (RS), both of which are already used in PV manufacturing — and its resultant optical and electronic properties. Final project goals were to test its application to Si and III-V solar cells. Controllable film thickness and excellent uniformity was established for both methods deposition methods, with ALD providing higher precision for thinner films and RS more effective for growing thicker films. The as-deposited films were found to be amorphous in nature. Spectroscopic ellipsometry (SE) confirmed bandgaps of at least 4.8 eV and non-parasitic absorption across both AM0 and AM1.5G spectra; a refractive index approaching the expected value of 1.8 was also observed, with some degree of tunability based on process parameters. Using this initial optical data, a transfer matrix model, which interfaces with in-house EQE and LIV models, was developed to simulate Ga 2 O 3 optical effects on various solar cells, included potential in antireflection coatings (ARCs). Despite promising optical properties, the resultant resistivity / conductivity metrics did not meet expectations, regardless of deposition process. Although thick RS-deposited films, using both undoped and 1 at% Ge (n-type) doped sintered targets — demonstrated high net carrier concentrations (via C-V), and low specific resistance Ohmic contacts were demonstrated, transmission line measurements (TLM) showed very high resistivity. Further analysis indicated high vertical film conductivity, but very low lateral conductivity. Deeper characterization revealed a relatively high density of nano/microcrystalline inclusions that were ostensibly the source of the vertical conductivity, with the amorphous matrix serving as an effective insulator (likely due to high concentrations of electronic trap states). Despite extensive work to increase film polycrystallinity — demonstrated via high temperature annealing — sufficient lateral conductivity for TCO use was not achieved. The final phase of the project shifted focus toward investigation of ALD-deposited Ga 2 O 3 ’s potential as a passivant and/or passivating contact for both Si and III-V solar cells, with expectation of performance similar to Al 2 O 3 . However, initial rounds of testing using our baseline ALD process yielded minimal (but not quite zero) passivation of both GaInP and Si surfaces. Dielectric passivation is well-known to be highly process sensitive; given the unoptimized nature of the process used, this work was deemed inconclusive. The final outlook with respect to feasibility of Ga 2 O 3 as a PV-oriented TCO is, ultimately, still uncertain. The work performed in this project confirmed the optical properties and deposition methods, but the achieved electrical properties do not meet technological needs; literature reports in recent years are somewhat inconsistent and potentially untrustworthy, but generally appear to be in line with our results. At the very least it is clear that, should Ga 2 O 3 still be under consideration for PV TCO and/or selective contact applications, a significant amount of optimization and study is still needed.

14 SOLAR ENERGY↗

Gamma-Ray, Cosmic Ray and Neutrino Tests of Lorentz Invariance and Quantum Gravity Models

High-energy astrophysics observations provide the best possibilities to detect a very small violation of Lorentz invariance such as may be related to the structure of space-time near the Planck scale of approximately 10(exp -35) m. I will discuss here the possible signatures of Lorentz invariance violation (LIV) from observations of the spectra, polarization, and timing of gamma-rays from active galactic nuclei and gamma-ray bursts. Other sensitive tests are provided by observations of the spectra of ultrahigh energy cosmic rays and neutrinos. Using the latest data from the Pierre Auger Observatory one can already derive an upper limit of 4.5 x 10(exp -23) to the amount of LIV of at a proton Lorentz factor of approximately 2 x 10(exp 11). This result has fundamental implications for quantum gravity models. I will also discuss the possibilities of using more sensitive space based detection techniques to improve searches for LIV in the future.

Stecker, Floyd↗

Testing effects of Lorentz invariance violation in the propagation of astroparticles with the Pierre Auger Observatory

Lorentz invariance violation (LIV) is often described by dispersion relations of the form E i 2 = m i 2 +p i 2 +δ i,n E 2+n with delta different based on particle type i , with energy E, momentum p and rest mass m. Kinematics and energy thresholds of interactions are modified once the LIV terms become comparable to the squared masses of the particles involved. Thus, the strongest constraints on the LIV coefficients δ i,n tend to come from the highest energies. At sufficiently high energies, photons produced by cosmic ray interactions as they propagate through the Universe could be subluminal and unattenuated over cosmological distances. Cosmic ray interactions can also be modified and lead to detectable fingerprints in the energy spectrum and mass composition observed on Earth. The data collected at the Pierre Auger Observatory are therefore possibly sensitive to both the electromagnetic and hadronic sectors of LIV. In this article, we explore these two sectors by comparing the energy spectrum and the composition of cosmic rays and the upper limits on the photon flux from the Pierre Auger Observatory with simulations including LIV. Constraints on LIV parameters depend strongly on the mass composition of cosmic rays at the highest energies. For the electromagnetic sector, while no constraints can be obtained in the absence of protons beyond 10 19 eV, we obtain δ γ,0 > -10 -21 , δ γ,1 > -10 -40 eV -1 and δ γ,2 > -10 -58 eV -2 in the case of a subdominant proton component up to 10 20 eV. For the hadronic sector, we study the best description of the data as a function of LIV coefficients and we derive constraints in the hadronic sector such as δ had,0 < 10 -19 , δ had,1 < 10 -38 eV -1 and δ had,2 < 10 -57 eV -2 at 5σ CL.

79 ASTRONOMY AND ASTROPHYSICS↗

Constraints on Lorentz Invariance Violation from Fermi -Large Area Telescope Observations of Gamma-Ray Bursts

We analyze the MeV/GeV emission from four bright Gamma-Ray Bursts (GRBs) observed by the Fermi-Large Area Telescope to produce robust, stringent constraints on a dependence of the speed of light in vacuo on the photon energy (vacuum dispersion), a form of Lorentz invariance violation (LIV) allowed by some Quantum Gravity (QG) theories. First, we use three different and complementary techniques to constrain the total degree of dispersion observed in the data. Additionally, using a maximally conservative set of assumptions on possible source-intrinsic spectral-evolution effects, we constrain any vacuum dispersion solely attributed to LIV. We then derive limits on the "QG energy scale" (the energy scale that LIV-inducing QG effects become important, E(sub QG)) and the coefficients of the Standard Model Extension. For the subluminal case (where high energy photons propagate more slowly than lower energy photons) and without taking into account any source-intrinsic dispersion, our most stringent limits (at 95% CL) are obtained from GRB 090510 and are E(sub QG,1) > 7.6 times the Planck energy (E(sub Pl)) and E(sub QG,2) > 1.3×10(exp 11) GeV for linear and quadratic leading order LIV-induced vacuum dispersion, respectively. These limits improve the latest constraints by Fermi and H.E.S.S. by a factor of approx. 2. Our results disfavor any class of models requiring E(sub QG,1) < or approx. E(sub Pl)

Planck↗

Constraints on Lorentz Invariance Violation from HAWC Observations of Gamma Rays above 100 TeV

Because of the high energies and long distances to the sources, astrophysical observations provide a unique opportunity to test possible signatures of Lorentz invariance violation (LIV). Superluminal LIV enables the decay of photons at high energy. The high altitude water Cherenkov (HAWC) observatory is among the most sensitive gamma-ray instruments currently operating above 10 TeV. HAWC finds evidence of 100 TeV photon emission from at least four astrophysical sources. These observations exclude, for the strongest of the limits set, the LIV energy scale to 2.2 × 10 31 eV , over 1800 times the Planck energy and an improvement of 1 to 2 orders of magnitude over previous limits.

79 ASTRONOMY AND ASTROPHYSICS↗

Quantitative comparison between sub-millisecond time resolution single-molecule FRET measurements and 10-second molecular simulations of a biosensor protein

Molecular Dynamics (MD) simulations seek to provide atomic-level insights into conformationally dynamic biological systems at experimentally relevant time resolutions, such as those afforded by single-molecule fluorescence measurements. However, limitations in the time scales of MD simulations and the time resolution of single-molecule measurements have challenged efforts to obtain overlapping temporal regimes required for close quantitative comparisons. Achieving such overlap has the potential to provide novel theories, hypotheses, and interpretations that can inform idealized experimental designs that maximize the detection of the desired reaction coordinate. Here, we report MD simulations at time scales overlapping with in vitro single-molecule Förster (fluorescence) resonance energy transfer (smFRET) measurements of the amino acid binding protein LIV-BP SS at sub-millisecond resolution. Computationally efficient all-atom structure-based simulations, calibrated against explicit solvent simulations, were employed for sampling multiple cycles of LIV-BP SS clamshell-like conformational changes on the time scale of seconds, examining the relationship between these events and those observed by smFRET. The MD simulations agree with the smFRET measurements and provide valuable information on local dynamics of fluorophores at their sites of attachment on LIV-BP SS and the correlations between fluorophore motions and large-scale conformational changes between LIV-BP SS domains. We further utilize the MD simulations to inform the interpretation of smFRET data, including Förster radius (R 0 ) and fluorophore orientation factor (κ 2 ) determinations. The approach we describe can be readily extended to distinct biochemical systems, allowing for the interpretation of any FRET system conjugated to protein or ribonucleoprotein complexes, including those with more conformational processes, as well as those implementing multi-color smFRET.

59 BASIC BIOLOGICAL SCIENCES↗

Searching for New Physics with Ultrahigh Energy Cosmic Rays

Ultrahigh energy cosmic rays that produce giant extensive showers of charged particles and photons when they interact in the Earth's atmosphere provide a unique tool to search for new physics. Of particular interest is the possibility of detecting a very small violation of Lorentz invariance such as may be related to the structure of space-time near the Planck scale of approximately 10 (exp -35) m. We discuss here the possible signature of Lorentz invariance violation on the spectrum of ultrahigh energy cosmic rays as compared with present observations of giant air showers. We also discuss the possibilities of using more sensitive detection techniques to improve searches for Lorentz invariance violation in the future. Using the latest data from the Pierre Auger Observatory, we derive a best fit to the LIV parameter of 3 .0 + 1.5 - 3:0 x 10 (exp -23) ,corresponding to an upper limit of 4.5 x 10-23 at a proton Lorentz factor of approximately 2 x 10(exp 11) . This result has fundamental implications for quantum gravity models.

Stecker, Floyd W.↗

Effects of Cage Type and NASA Rodent Food Bar in Male Sprague-Dawley Rats

Early prototype caging for the rodent Advanced Animal Habitat (P-AAH) for the International Space Station (ISS) is currently being tested. In this five week study, effects of the wire-bottom P-AAH cages and specialized NASA rodent food bars (FB) were compared to standard vivarium cages (VIV) with corn-cob, litter-filled bottoms, and standard Purina rat chow (CH). Ninety-six male Sprague-Dawley rats were divided into four treatment groups (24 rats/treatment): Group 1) VIV+CH, Group 2) P-AAH+CH, Group 3) VIV+FB, and Group 4) P-AAH+FB. Each VIV and P-AAH cage housed three and six rats, respectively. After five weeks of treatment rats were weighed, euthanized, and blood samples were collected. Weights of liver (LIV), kidney (KID), brain (BRN), epididymal fat (EPI), and perirenal fat (PERI) were also measured. Statistical analysis to compare differences between groups was performed by standard analysis of variance procedures (ANOVA) with a significance level of pLO.05. Results indicated P-AAH housed rats had significantly lower body weights (BW), LIV weights, and LIV/BW than VIV housed rats. FB fed rats had significantly lower blood urea nitrogen (BUN) levels and LIV/BW than CH fed rats. In addition, FB fed rats had significantly higher cholesterol (CHOL) levels, EPI/BW, PERI/BW, and total fat (EPI+PERI)/BW than CH fed rats. The P-AAH+FB group had significantly lower EPI, BRN, and total fat than VIV+FB rats. VIV+FB rats had significantly higher BRN, EPI, PERI, and total fat than VIV+CH rats. Triglycerides (TG), KID, KID/BW, and BRN/BW were not significantly different among treatment groups. These findings provide valuable information regarding cage design and food bar suitability for long-term use on the ISS.

Lau, Angela↗