High-Resolution X-ray Photoelectron Spectroscopy of an IrO2(110) Film on Ir(100)
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99 GENERAL AND MISCELLANEOUS↗
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Using Light to Enhance Charge Transfer in Battery Materials: Increasing Charging Rates in LiNi 0.5 Mn 1.5 O 4
Electrochemical, spectroscopic, and computational studies on the interplay between light perturbation and coupled electron and Li-ion transfer in LiNi 0.5 Mn 1.5 O 4 (LNMO) cathodes identify that photon perturbation moves the system out of equilibrium, increases entropy, lowers the impedance of the battery, and increases the charging capacity by at least 15% during fast charging by promoting the oxidation of Ni 3+ to Ni 4+ . Here, the correlation with density functional theory calculations points out that oxidation of Ni 3+ faces a 30% higher barrier compared with the oxidation of Ni 2+ and hence exhibits greater responses to the energy transferred from photons. Structural analysis elucidates that photon energy also assists the transition of LNMO from the Jahn−Teller distorted asymmetric lattice with Ni 3+ to the nondistorted Ni 4+ . Synergistically, photons energize the removal of electrons from Ni 3+ and create photoinduced Ni 4+ intermediates, followed by the removal of Li + with almost two times faster diffusion rates.
5 V spinel↗
Improving the Comprehensive Performance of Na 0.7 MnO 2 for Sodium Ion Batteries by ZrO 2 Atomic Layer Deposition
Sodium ion batteries with Na-Mn-O compounds as cathode have been widely studied as substitutes for lithium ion batteries due to their abundant resources. Still, the relatively poor cycling stability and low capacity of Na-Mn-O compounds significantly limit their applications. Different approaches, including element substitution and surface modification, have been applied to improve the electrochemical performance of those cathode materials. Herein, element doping and coating of ZrO 2 on Na 0.7 MnO 2 particles have been achieved by atomic layer deposition (ALD) followed by post-annealing. The rate capability and cycling stability of the modified material were significantly improved, and the mechanism of performance enhancement was revealed. The ZrO 2 coatings acted as a stable interfacial layer to enhance the cycling stability of Na 0.7 MnO 2 by suppressing side reactions between the electrode and electrolyte. The doping of transition metal ions reduced energy barriers for sodium ion insertion and deintercalation during cycling, further improving the charge and discharge capacity and rate performance of Na 0.7 MnO 2 .
25 ENERGY STORAGE↗
Unraveling the CO Oxidation Mechanism over Highly Dispersed Pt Single Atom on Anatase TiO 2 (101)
Catalysts with noble metals deposited as single atoms on metal oxide supports have recently been studied extensively due to their maximized metal utilization and potential for performing difficult chemical conversions owing to their unique electronic properties. Understanding of the reaction mechanisms on supported single-metal atoms is still limited but is highly important for designing more efficient catalysts. In this study, we report the complexity of the CO oxidation reaction mechanism on Pt single atoms supported on anatase TiO 2 (Pt SA /a-TiO 2 ) by coupling density functional theory (DFT) calculations and microkinetic analysis with kinetic measurements, in situ/operando infrared, and X-ray absorption spectroscopies. Starting from the adsorbed Pt SA occupying an O vacancy induced by reductive pretreatment, we show that CO oxidation follows a complex mechanism consisting of initiation steps to reorganize the active site and multibranch reactive cycles, with the Pt SA /a-TiO 2 catalyst not returning to its initial configuration. The initiation step consists of CO and O 2 adsorption healing the O vacancy, followed by CO oxidation using gas-phase CO to form Pt(CO). The reactive cycle alternates O 2 adsorption and dissociation to oxidize the catalyst to Pt(O)(O)(CO) and branching pathways of competing Langmuir–Hinshelwood (LH)- or Eley–Rideal (ER)-type CO oxidation steps to reduce it again to Pt(CO). In situ/operando infrared experiments, including cryogenic CO adsorption and isotopic CO exchange, confirm the combined involvement of strongly adsorbed CO and gas-phase CO in an Eley–Rideal step along the reaction cycle. Microkinetic modeling shows that Pt single atoms are present in a mixture of Pt(CO), Pt(CO)(O 2 ), Pt(O)(CO)(O 2 ), and Pt(CO)(CO 3 ) structures as the main intermediates during steady-state CO oxidation, all having the C–O vibrational stretch close to the experimentally observed value of 2115 cm –1 . Microkinetic modeling also shows that the fractional orders of CO and O 2 measured experimentally originate from multiple steps with a high degree of rate control and not from a simple competitive adsorption. The results demonstrate the complex reaction pathways that even CO oxidation on a simple single-atom system can follow, providing mechanistic insights for designing efficient Pt-based single-atom catalysts. Here, we further show that microkinetic modeling results are sensitive to changes in energies of intermediate and transition states within errors of density functional theory, which can ultimately lead to incorrect conclusions regarding the reaction pathways and most abundant reaction intermediates if not accounted for by experiments.
36 MATERIALS SCIENCE↗
Anomalous lattice thermal conductivity increase with temperature in cubic GeTe correlated with strengthening of second-nearest neighbor bonds
Understanding thermal transport mechanisms in phase change materials is critical to elucidating the microscopic picture of phase transitions and advancing thermal energy conversion and storage. Experiments consistently show that cubic phase germanium telluride (GeTe) has an unexpected increase in lattice thermal conductivity with rising temperature. Despite its ubiquity, resolving its origin has remained elusive. In this work, we carry out temperature-dependent lattice thermal conductivity calculations for cubic GeTe through efficient, high-order machine-learned models and additional corrections for coherence effects. We corroborate the calculated phonon properties with our inelastic X-ray scattering measurements. Our calculated lattice thermal conductivity values agree well with experiments and show a similar increasing trend. Through additional bonding strength calculations, we propose that a major contributor to the increasing lattice thermal conductivity is the strengthening of second-nearest neighbor interactions. The findings herein serve to deepen our understanding of thermal transport in phase-change materials.
36 MATERIALS SCIENCE↗
Theory of superconductivity in doped quantum paraelectrics
Abstract Recent experiments on Nb-doped SrTiO 3 have shown that the superconducting energy gap to the transition temperature ratio maintains the Bardeen–Cooper–Schrieffer (BCS) value throughout its superconducting dome. Motivated by these and related studies, we show that the Cooper pairing mediated by a single soft transverse-optical phonon is the most natural mechanism for such a superconducting dome given experimental constraints, and present the microscopic theory for this pairing mechanism. Furthermore, we show that this mechanism is consistent with the T 2 resistivity in the normal state. Lastly, we discuss what physical insights SrTiO 3 provides for superconductivity in other quantum paraelectrics such as KTaO 3 .
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Curie-Weiss behavior of liquid structure and ideal glass state
We present the results of a structural study of metallic alloy liquids from high temperature through the glass transition. We use high energy X-ray scattering and electro-static levitation in combination with molecular dynamics simulation and show that the height of the first peak of the structure function, S(Q) -1, follows the Curie-Weiss law. The structural coherence length is proportional to the height of the first peak, and we suggest that its increase with cooling may be related to the rapid increase in viscosity. The Curie temperature is negative, implying an analogy with spin-glass. The Curie-Weiss behavior provides a pathway to an ideal glass state, a state with long-range correlation without lattice periodicity, which is characterized by highly diverse local structures, reminiscent of spin-glass.
36 MATERIALS SCIENCE↗
Direct genome-scale screening of Gluconobacter oxydans B58 for rare earth element bioleaching
Abstract The transition to a sustainable energy economy will require an enormous increase in the supply of rare earth elements (REEs). Bioleaching offers a promising alternative to conventional hydrometallurgical methods for REE extraction from low-grade ores. However, exploiting this potential remains challenging due to large gaps in our understanding of the genetics involved, and inadequate biological tools to address them. We generated a highly non-redundant whole-genome knockout collection for the bioleaching microbe Gluconobacter oxydans B58, reducing redundancy by 85% compared to the previous best collection. This new collection was directly screened for bioleaching neodymium from a synthetic monazite powder, identifying 89 genes important for bioleaching, 68 of which have not previously been associated with this mechanism. We conducted bench-scale experiments to validate the extraction efficiency of promising strains: 8 demonstrated significant increases in extraction by up to 111% (δ GO_1598 , disruption of the gene encoding the orotate phosphoribosyltransferase enzyme PyrE), and one strain significantly reduced it by 97% (δ GO_1096 , disruption of the gene encoding the GTP-binding protein TypA). Notable changes in pH were only observed for 3 strains, suggesting an important role for non-acid mechanisms in bioleaching. These findings provide valuable insights into further enhancing REE-bioleaching by G. oxydans through genetic engineering.
Marecos, Sabrina (ORCID:0000000158529933)↗
Trends in actinide electronic structure revealed from asymmetric, isostructural transuranic metallocenes
The study of actinide electronic structure and bonding within rigorously controlled environments is fundamental to advancing nuclear applications. Here, we report a new set of isostructural actinide organometallics; An(COT big ) 2 , (An = Th, U, Np, and Pu), where COT big is the bulky 1,4-bis(triphenylsilyl)-substituted cyclooctatetraenyl dianion (1,4-(Ph 3 Si) 2 C 8 H 6 ) 2 -. The actinide(IV) metallocene sandwiches have a clam-shell structure, offering a new molecular symmetry to explore f-orbital contributions in bonding. Combined experimental and computational studies reveal that An(COT big ) 2 complexes strongly differ from the previously published coplanar An(COT) 2 sandwiches due to the bent geometry and electron-withdrawing nature of the substituents. While COT big displays comparatively weaker electron donation, the low-energy f-f transitions in An(COT big ) 2 have increased molar absorptivity consistent with the removal of the parity selection rule and better energetic matching between ligand and actinide 5f orbitals as the series is traversed. For Pu(COT big ) 2 , covalent mixing of donor 5f metal orbitals and the ligand-π orbitals is especially strong.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Mechanistic investigation of a visible light mediated dehalogenation/cyclisation reaction using iron( iii ), iridium( iii ) and ruthenium( ii ) photosensitizers
The mechanism of a visible light-driven dehalogenation/cyclization reaction was investigated using ruthenium(II), iridium(III) and iron(III) photosensitizers by means of steady-state photoluminescence, time-resolved infrared spectroscopy, and nanosecond/femtosecond transient absorption spectroscopy. The nature of the photosensitizer was found to influence the product distribution such that the dehalogenated, non-cyclized products were only detected for the iron photosensitizer. Strikingly, with the iron photosensitizer, large catalytic yields required a low dielectric solvent such as dichloromethane, consistent with a previous publication. This low dielectric solvent allowed ultrafast charge-separation to outcompete geminate charge recombination and improved cage escape efficiency. Finally, the identification of reaction mechanisms unique to the iron, ruthenium, and iridium photosensitizer represents progress towards the long-sought goal of utilizing earth-abundant, first-row transition metals for emerging energy and environmental applications.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Structural coupling and magnetic tuning in Mn 2– x Co x P magnetocalorics for thermomagnetic power generation
Promising materials for magnetic refrigeration and thermomagnetic power generation often display strong coupling between magnetism and structure. It has been previously proposed that MnCoP exhibits this strong coupling, contributing to its substantial magnetocaloric effect near T C = 578K. Here, we show from temperature-dependent synchrotron x-ray diffraction that MnCoP displays a discontinuity in the thermal expansion at T C , with spontaneous magnetostriction that is positive in the a direction and negative in the b direction, highlighting the anisotropic nature of the magnetostructural coupling. Varying the Mn:Co ratio of Mn 2– x Co x P within the range of 0.6 ≤ x ≤ 1.4 allows the magnetic properties to be tuned. T C decreases as the composition deviates from stoichiometric MnCoP, as does the saturation magnetization. The magnitude of the magnetocaloric effect, |Δ S M |, decreases as well, due to broadening of the magnetic transition. The large reversible change in magnetization Δ M accessible over a small temperature range under moderate magnetic fields makes these materials promising for thermomagnetic power generation from waste heat.
36 MATERIALS SCIENCE↗
Ultraviolet photodissociation of gas-phase iron pentacarbonyl probed with ultrafast infrared spectroscopy
It is well known that ultraviolet photoexcitation of iron pentacarbonyl results in rapid loss of carbonyl ligands leading to the formation of coordinatively unsaturated iron carbonyl compounds. Here we employ ultrafast mid-infrared transient absorption spectroscopy to probe the photodissociation dynamics of gas-phase iron pentacarbonyl following ultraviolet excitation at 265 and 199 nm. After photoexcitation at 265 nm, our results show evidence for sequential dissociation of iron pentacarbonyl to form iron tricarbonyl via a short-lived iron tetracarbonyl intermediate. Photodissociation at 199 nm results in the prompt production of Fe(CO) 3 within 0.25 ps via several energetically accessible pathways. An additional 15 ps time constant extracted from the data is tentatively assigned to intersystem crossing to the triplet manifold of iron tricarbonyl or iron dicarbonyl. Mechanisms for formation of iron tetracarbonyl, iron tricarbonyl, and iron dicarbonyl are proposed and theoretically validated with one-dimensional cuts through the potential energy surface as well as bond dissociation energies. Ground state calculations are computed at the CCSD(T) level of theory and excited states are computed with EOM-EE-CCSD(dT).
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Transient hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation. II. Isomer-resolved unimolecular dynamics
Transient carbon-centered hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation are characterized by their time- and energy-resolved unimolecular dissociation dynamics to hydroxyl (OH) and cyclic ether products. Two distinct •QOOH isomers are examined with radical sites at a primary carbon of one of the methyl groups (β-Me) or a secondary carbon (β-Et) of the ethyl group. Energy-dependent unimolecular rates are obtained from the time-dependent appearance of OH products for the two isomers and compared with statistical microcanonical rates computed using RRKM theory, including heavy-atom tunneling, based on high-level theoretical calculations. A benchmark-corrected approach is utilized to compute high-accuracy stationary-point energies, most importantly, transition-state barriers, for the •QOOH_Me and •QOOH_Et isomers in isopentane oxidation, building on higher-level reference calculations for the oxidation of ethane (C 2 H 5 O 2 ) and propane (C 3 H 7 O 2 ), respectively. Here, the measured rates are compared with RRKM calculations incorporating the benchmark-corrected transition-state parameters, a vibrationally adiabatic multidimensional hindered-rotor treatment of key torsions, and quantum tunneling. Agreement between experiment and theory validates the statistical description and shows faster decay for •QOOH_Et due to its lower barrier. Both β-QOOH isomers decay almost exclusively to OH + cyclic ether products under the conditions studied.
Oxidation processes↗
What are grana in chloroplasts of vascular plants good for?
All plants and green algae contain stacked grana thylakoid membranes in their chloroplasts, underscoring an evolutionary pressure to maintain this unique structural feature. In addition, numerous studies have demonstrated that particular lateral and vertical dimensions of grana facilitate the function, regulation and repair of the photosynthetic machinery responsible for energy conversion. In this review, we present an updated overview of our understanding concerning the structure of grana thylakoids, the forces that contribute to their formation and their architectural dynamics. After establishing the structural foundation, we continue by reviewing the implications of grana formation on light harvesting, electron transport and protein maintenance in the thylakoid membranes of vascular plants. Regarding light harvesting, we discuss the implications of grana formation on energy spillover, macromolecular crowding, lateral versus vertical excitation energy transfer, and state transition. With respect to electron transport, we summarize recent findings regarding the functional connectivity of spatially separated photosystems facilitated by grana formation through small mobile electron carriers. We also explore how the dynamic responses of grana architecture regulate electron transport. Finally, we address how grana formation contributes to the organization of protein repair and biogenesis within thylakoid membranes.
59 BASIC BIOLOGICAL SCIENCES↗
Detonation-induced transformation of graphite to hexagonal diamond
In this work, we explore the structural evolution of highly oriented pyrolytic graphite (HOPG) under detonation-induced shock conditions using in situ synchrotron x-ray diffraction in the ns timescale. We observe the formation of hexagonal diamond (lonsdaleite) at pressures above 50 GPa, in qualitative agreement with recent gas gun experiments. First-principles density functional calculations reveal that under uniaxial compression, the energy barrier for the transition toward hexagonal diamond is lower than that for cubic diamond. Finally, no indication of cubic diamond formation was observed up to >70 GPa.
36 MATERIALS SCIENCE↗
First β-decay spectroscopy of 135 In and new β-decay branches of 134 In
The β decay of the neutron-rich 134 In and 135 In was investigated experimentally in order to provide new insights into the nuclear structure of the tin isotopes with magic proton number Z=50 above the N=82 shell. The β-delayed γ-ray spectroscopy measurement was performed at the ISOLDE facility at CERN, where indium isotopes were selectively laser-ionized and on-line mass separated. Three β-decay branches of 134 In were established, two of which were observed for the first time. Population of neutron-unbound states decaying via γ rays was identified in the two daughter nuclei of 134 In, 134 Sn and 133 Sn, at excitation energies exceeding the neutron separation energy by 1 MeV. The β-delayed one- and two-neutron emission branching ratios of 134 In were determined and compared with theoretical calculations. The β-delayed one-neutron decay was observed to be dominant β-decay branch of 134 In even though the Gamow-Teller resonance is located substantially above the two-neutron separation energy of 134 Sn. Transitions following the β decay of 135 In are reported for the first time, including γ rays tentatively attributed to 135 Sn. In total, six new levels were identified in 134 Sn on the basis of the βγγ coincidences observed in the 134 In and 135 Inβ decays. A transition that might be a candidate for deexciting the missing neutron single-particle 13/2 + state in 133 Sn was observed in both β decays and its assignment is discussed. Experimental level schemes of 134 Sn and 135 Sn are compared with shell-model predictions. Using the fast timing technique, half-lives of the 2 + , 4 + , and 6 + levels in 134 Sn were determined. From the lifetime of the 4 + state measured for the first time, an unexpectedly large B(E2;4 + → 2 + ) transition strength was deduced, which is not reproduced by the shell-model calculations.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
First β -delayed neutron spectroscopy of 24 O
The β decay of 24 O was investigated at NSCL/MSU using a combination of neutron and γ-ray spectroscopy. For the first time, the β-delayed neutron energy spectrum of 24 O was measured, revealing three intensely populated, isolated neutron-unbound states in 24 F. This allowed for the extraction of the decay strength in 24 F up to 6.2 MeV. A comprehensive comparison of the experimental results with various nuclear theories, ranging from the empirical shell model to the most advanced ab initio calculations, was conducted. While most theoretical predictions align with the experimental data for low-lying states, discrepancies arise at higher excitation energies. Finally, in the transition from 24 O to 24 F, shell model calculations using the empirical USDB interaction predicted the structure of both nuclei without invoking the need for a stronger proton-neutron tensor force, which was postulated for the neighboring isotone 25 F.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
Quantifying Risk in an Uncertain Future: The Evolution of Resource Adequacy
As our power grids transition toward a decarbonized energy mix, ensuring reliability and provision of grid services remains paramount. The power system has always been heavily influenced by the weather - extreme temperatures determine the timing of peak demand, winter cold snaps can limit natural gas supply, gas turbine reliability and output are affected by ambient conditions, and hydro output varies seasonally and annually. However, as the grid increasingly relies on variable renewable energy (VRE), like wind and solar, the attention to reliability and weather conditions is increasingly important. The implications of changing reliability are large. The Electric Reliability Council of Texas (ERCOT) rolling blackouts from earlier this year impacted millions of people across the state and could be seen from space (Figure 1).
hydraulic turbines↗