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At least 289 records · Page 16

Decoupling of catalysis and transition state analog binding from mutations throughout a phosphatase revealed by high-throughput enzymology

Using high-throughput microfluidic enzyme kinetics (HT-MEK), we measured over 9,000 inhibition curves detailing impacts of 1,004 single-site mutations throughout the alkaline phosphatase PafA on binding affinity for two transition state analogs (TSAs), vanadate and tungstate. As predicted by catalytic models invoking transition state complementary, mutations to active site and active-site-contacting residues had highly similar impacts on catalysis and TSA binding. Unexpectedly, most mutations to more distal residues that reduced catalysis had little or no impact on TSA binding and many even increased tungstate affinity. These disparate effects can be accounted for by a model in which distal mutations alter the enzyme’s conformational landscape, increasing the occupancy of microstates that are catalytically less effective but better able to accommodate larger transition state analogs. In support of this ensemble model, glycine substitutions (rather than valine) were more likely to increase tungstate affinity (but not more likely to impact catalysis), presumably due to increased conformational flexibility that allows previously disfavored microstates to increase in occupancy. These results indicate that residues throughout an enzyme provide specificity for the transition state and discriminate against analogs that are larger only by tenths of an Ångström. Thus, engineering enzymes that rival the most powerful natural enzymes will likely require consideration of distal residues that shape the enzyme’s conformational landscape and fine-tune active-site residues. Biologically, the evolution of extensive communication between the active site and remote residues to aid catalysis may have provided the foundation for allostery to make it a highly evolvable trait.

59 BASIC BIOLOGICAL SCIENCES↗

Coupled Heat Power Operation of Smart Buildings via Modular Pumped Hydro Storage

In the United States, building sector is responsible for around 40% of total energy consumption and contributes about 40% of carbon emissions since 2012. Within the past several years, various optimization models and control strategies have been studied to improve buildings’ energy efficiency and reduce operational expenses under the constraints of satisfying occupants’ comfort requirements. However, the majority of these studies consider building electricity demand and thermal load being satisfied by unidirectional electricity flow from the power grid or on-site renewable energy generation to electrical and thermal home appliances. Opportunities for leveraging low-grade heat for electricity have largely been overlooked due to impracticality at small scale. In 2016, a modular pumped hydro storage technology was invented in Oak Ridge National Laboratory, named Ground Level Integrated Diverse Energy Storage (GLIDES). In GLIDES, employing high-efficiency hydraulic machinery instead of gas compressor/turbine, liquid is pumped to compress gas inside high-pressure vessel creating head on ground level. This unique design eliminates the geographical limitation associated with the existing state-of-the-art energy storage technologies. It is easy to be scaled for building level, community level, and grid level applications. By using this novel hydro-pneumatic storage technology, opportunities for leveraging low-grade heat in building can be economical. In this research, the potential of utilizing low-grade thermal energy to augment electricity generation of GLIDES is investigated. Since GLIDES relies on gas expansion in the discharge process and the gas temperature drops during this non-isothermal process, available thermal energy, e.g., from thermal storage, combined cooling, heat and power system (CCHP), can be utilized by GLIDES to counter the cooling effect of the expansion process and elevate the gas temperature and pressure and boost the roundtrip efficiency. Here, several groups of comparison experiments have been conducted, and the experimental results show that a maximum 12.9% cost saving could be achieved with unlimited heat source for GLIDES, and a moderate 3.8% cost improvement can be expected when operated coordinately with CCHP and thermal energy storage in a smart building.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Heat Based Power Augmentation for Modular Pumped Hydro Storage in Smart Buildings Operation

In the U.S., building sector is responsible for around 40% of total energy consumption and contributes about 40% of carbon emissions since 2012. Within the past several years, various optimization models and control strategies have been studied to improve buildings energy efficiency and reduce operational expenses under the constraints of satisfying occupants’ comfort requirements. However, the majority of these studies consider building electricity demand and thermal load being satisfied by unidirectional electricity flow from the power grid or on-site renewable energy generation to electrical and thermal home appliances. Opportunities for leveraging low grade heat for electricity have largely been overlooked due to impracticality at small scale. In 2016, a modular pumped hydro storage technology was invented in Oak Ridge National Laboratory, named Ground Level Integrated Diverse Energy Storage (GLIDES). In GLIDES, employing high efficiency hydraulic machinery instead of gas compressor/turbine, liquid is pumped to compress gas inside high-pressure vessel creating head on ground-level. This unique design eliminates the geographical limitation associated with existing state of the art energy storage technologies. It is easy to be scaled for building level, community level and grid level applications. Using this novel hydro-pneumatic storage technology, opportunities for leveraging low-grade heat in building can be economical. In this research, the potential of utilizing low-grade thermal energy to augment electricity generation of GLIDES is investigated. Since GLIDES relies on gas expansion in the discharge process and the gas temperature drops during this non-isothermal process, available thermal energy, e.g. from thermal storage, Combined Cooling, Heat and Power system (CCHP), can be utilized by GLIDES to counter the cooling effect of the expansion process and elevate the gas temperature and pressure and boost the roundtrip efficiency. Several groups of comparison experiments have been conducted and the experimental results show that a maximum 12.9% cost saving could be achieved with unlimited heat source for GLIDES, and a moderate 3.8% cost improvement can be expected when operated coordinately with CCHP and thermal energy storage in a smart building.

Chen, Yang↗

DFT Plus DMFT Study of Spin-Charge-Lattice Coupling in Covalnt LaCoO{siub 3}.

We study energetics and the nature of both homogeneous and mixed spin (MS) states in LaCoO3 incorporating structural changes of the crystal volume expansion and the Co-O bond disproportionation (BD) during the spin-state transition using the density functional theory plus dynamical mean field theory (DFT + DMFT) method. DFT + DMFT predicts that energetics of both excited spin states are almost the same while DFT + U calculations of the same structures energetically favor the MS states and produce various metastable solutions whose energetics depend sensitively on final spin states. Within DFT + DMFT, the homogeneous spin state in the expanded crystal volume shows the multiconfigurational nature with non-negligible occupancy probabilities of both high spin (HS) and low spin (LS) states along with d(6) and d(7) charge configurations indicating the dynamically fluctuating nature of spin and charge states due to the Co-O covalency. The nature of the MS state under the BD structure reveals that Co sites with the long Co-O bonds develop a Mott insulating state and favor HS with a d(6) configuration, while more covalent Co sites with the short Co-O bonds occupy more LS states with a d(7) configuration and behave as a band insulator, as a result, charge ordering is induced in the BD structure from the spin-state ordering. We also find that both energetics and electronic structure sensitively depend on the Co-O covalency effect, which can be tuned by changing the double counting potential and the resulting d occupancy (N-d), and N-d close to 6.7 is consistent with the nature of the spin-state transition. Our results show that structural changes during the spin-state transition can play an important role in understanding energetics and electronic structure of LaCoO3.

Park, Hyowon↗

Structure of a photosystem I-ferredoxin complex from a marine cyanobacterium provides insights into far-red light photoacclimation

Far-red light photoacclimation (FaRLiP) exhibited by some cyanobacteria allows these organisms to use light of the far-red region of the solar spectrum (700 to 800 nm) for photosynthesis. Part of this process includes the replacement of six photosystem I (PSI) subunits with isoforms that confer the binding of chlorophyll (Chl) f molecules that are synthesized by chlorophyll f synthase and that absorb far-red light. However, the exact sites at which Chl f molecules are bound are still challenging to determine. To aid in the identification of Chl fbinding sites, we solved the cryo-EM structure of PSI from far-red light-acclimated cells (FRLPSI) of the cyanobacterium Synechococcus sp. PCC 7335. We identified six sites that bind Chl f with high specificity, and three additional sites that are likely to bind Chl f at lower specificity. All of these binding sites are in the core antenna regions of PSI, and Chl f was not observed among the electron transport cofactors. This structural analysis also reveals both conserved and non-conserved Chl f-binding sites, the latter of which exemplify the diversity in FRL-PSI among species. We found that the FRL-PSI structure also contains a bound soluble ferredoxin, PetF1, at low occupancy, which suggests that ferredoxin binds less transiently than expected according to the canonical view of ferredoxin-binding to facilitate electron transfer. We suggest that this may result from structural changes in FRL-PSI that occur specifically during FaRLiP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hanford Site Bee Nest Box Monitoring Report for Calendar Year 2019

This report summarizes the results of the first year of monitoring bee nest boxes on the Hanford Site. Twenty bee nest boxes were installed as a component of compensatory mitigation for the installation of the L-894 water line between the 200-East and 200-West Areas of the Hanford Site. The goal of this compensatory mitigation is to replace lost nesting habitat for above-ground nesting bees in a mature sagebrush ecosystem. Annual monitoring will track the condition and occupation of the bee nest boxes to determine if the compensatory mitigation was successful and to identify best practices when replacing nesting habitat for native bees.

54 ENVIRONMENTAL SCIENCES↗

LANL Regular Employee Population and Demographics, FY15-21

This document summarizes an effort to compile and analyze the LANL regular employee population’s demographic attributes and trends between FY15-FY21 using MicroStrategy, a web-based data analytics and visualization tool. LANL’s HR Division collected and prepared data for the Weapons Program’s annual reporting activities for the 2017 through 2023 NNSA Stockpile Stewardship and Management Plan (SSMP). Los Alamos workforce data represent the fiscal year-end snapshot of the permanent employee population who are categorized by the Common Occupational Classification System (COCS). This work enables further analyses, including trends for all workforce attributes presented in the SSMPs as well as a definition of a crosswalk between COCS categorization and the internal laboratory job classification hierarchy. Data for other sites and the federal workforce, as shown in the SSMPs, are included and corresponding figures can be visualized within the MicroStrategy tool. A portable, Excel-based version of the tool was developed and shared with the multi-site workforce working group. This summary highlights selected aspects of the LANL regular workforce. The data analyses and visualizations communicate insights within three major themes regarding permanent LANL employees: 1) demographic transformation, 2) attrition, and 3) skills. Regarding demographic transformation, and consistent with the general trend across the enterprise, early career regular employees are the fastest growing group, with growth ranging between 12-34% year-to-year over the seven-year period analyzed. The data also reflect effects of internal and external factors on attrition; the large spike in separations in FY18 aligns with the contract transition from LANS to Triad and the dip in attrition between FY20-FY21 is likely a result of the global pandemic. The population of regular employees in general management, engineer, and operator COCS categories have the fastest growth rates amongst all the occupational categories. The MicroStrategy and Excel tools provide additional details and trends.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Residential Building Energy Efficiency Field Studies: Low-Rise Multifamily

In recent years, the U.S. Department of Energy (DOE) has conducted a series of research studies to validate energy efficient building technologies in the field. Much of the work has focused on single-family construction, and some has also addressed commercial energy codes. The work detailed in this DOE-funded study (EE0007616) focuses on low-rise multifamily buildings (three stories or fewer above grade) in various regions of the United States, and reports on how state-level building codes are being implemented, both in terms of observed characteristics and also in terms of estimated energy impacts. Nearly 100 buildings across four states—Illinois, Minnesota, Oregon, and Washington—were sampled, which represent a range of climate types from mild temperature to very cold continental. Both common entry and outdoor entry buildings were included, and a parallel research project evaluated envelope air tightness and current still-evolving air tightness testing methods. Finally, a set of structured interviews of building designers and other relevant professionals was carried to out to gain more insight into this market. To the greatest extent possible, the methodology developed under the project for low-rise multifamily buildings mirrored the approach established by Pacific Northwest National Laboratory (PNNL) for single-family residential buildings (https://www.energy.gov/eere/buildings/downloads/residential-building-energy-code-field-study). This included the general approach to sampling, recruitment, and data collection, as well as data analysis and presentation. The range of permitting dates for the sites encompassed two energy code cycles in most regions. All states in the study had adopted a variation of the International Energy Conservation Code (IECC) for the structure of their state code. The low-rise multifamily occupancy presents a hybrid building type: most of the building’s conditioned floor area was covered by the residential chapter of the code while portions of the building (such as corridors and common spaces) fell under the commercial code chapter. The key items assessed in this work were: Building Shell—exterior wall insulation, ceiling insulation, foundation insulation, windows. Common Areas—HVAC and lighting. Living Units—lighting, ventilation. A few items were not assessed in detail, given their relative paucity in this occupancy type; these included duct leakage, pipe insulation, and hot water circulation controls. Building characteristics were collected via a combination of architectural, mechanical, electrical, and plumbing plan reviews and field inspections, and entered into a spreadsheet-based tool that was later queried to build a database. Data went through quality control both upon arrival and via a later semi-automated review and assurance process. Most of the data are presented graphically so that the reader can quickly assess compliance with the applicable energy codes (both by state and by code year). As a final step, EnergyPlus™ simulations were created for all buildings in the study to estimate both the as-found energy use intensity (EUI) and the energy and CO 2 that could be saved if features that were found to not meet code minimums were brought up to code. The savings estimates were tabulated for each of the four states in the study. The research team found that the single-family approach was largely applicable to low-rise multifamily buildings. This applies to both the data collection and the prototype EUI analysis. Most of the occupied space is living units and falls under residential energy codes, and many characteristics use similar envelope construction and relatively straightforward mechanical systems and lighting. One of the most challenging aspects of this work was to build an effective spreadsheet-based data collection instrument that could allow efficient collection of both building plan and field data. The research team is of the view that other methods could be equally effective if the work is done carefully with diligent quality control. The primary findings for the work center around the thermal envelope and mechanical systems and lighting at the sites: For thermal envelope components, the majority of buildings met or were better than the prescriptive code.This suggests that building designers and builders are aware of code requirements. In some cases, surveyed buildings were designed to qualify for energy efficiency certification programs. These buildings made up at least 20% of sampled buildings in each state. Almost all buildings met mechanical system efficiency requirements (for both living units and common areas). In some cases, sites employed systems that were considerably more efficient than required by the applicable energy code. Dwelling units had a majority of high-efficacy lighting, often in excess of the state’s residential code requirements. While high-efficacy fixtures were also typical in common areas (corridors and stairwells), lighting power densities (LPDs) in these areas were sometimes higher than levels dictated by the applicable part of the state commercial energy code. The simulation models run on a series of low-rise multifamily prototypes, informed by a composite of the field data collected, calculated annual EUIs of between 20 and 50 kBtu/ft2-yr, with the range representing the effects of both building characteristics and building location (climate zone). A detailed process (based on simulations of prototype buildings) was used to estimate the amount of avoided energy use that would occur if 100% adherence to energy codes were attained. The results indicated modest savings are attainable for items such as window thermal performance and common area lighting. The result is overall only a modest potential for additional energy savings, averaging about 10% of EUI.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Engineered Solutions to Reduce Occupational Noise Exposure at the NASA Glenn Research Center: A Five-Year Progress Summary (1994-1999)

At the NASA John H. Glenn Research Center at Lewis Field (formerly the Lewis Research Center), experimental research in aircraft and space propulsion systems is conducted in more than 100 test cells and laboratories. These facilities are supported by a central process air system that supplies high-volume, high-pressure compressed air and vacuum at various conditions that simulate altitude flight. Nearly 100,000 square feet of metalworking and specialized fabrication shops located on-site produce prototypes, models, and test hardware in support of experimental research operations. These activities, comprising numerous individual noise sources and operational scenarios, result in a varied and complex noise exposure environment, which is the responsibility of the Glenn Research Center Noise Exposure Management Program. Hearing conservation, community noise complaint response and noise control engineering services are included under the umbrella of this Program, which encompasses the Occupational Safety and Health Administration (OSHA) standard on occupational noise exposure, Sec. 29CFR 1910.95, as well as the more stringent NASA Health Standard on Hearing Conservation. Prior to 1994, in the absence of feasible engineering controls, strong emphasis had been placed on personal hearing protection as the primary mechanism for assuring compliance with Sec. 29CFR 1910.95 as well as NASA's more conservative policy, which prohibits unprotected exposure to noise levels above 85 dB(A). Center policy and prudent engineering practice required, however, that these efforts be extended to engineered noise controls in order to bring existing work areas into compliance with Sec. 29CFR 1910.95 and NASA's own policies and to ensure compliance for new installations. Coincident with the establishment in 1995 of a NASA wide multi-year commitment of funding for environmental abatement projects, the Noise Exposure Management Program was established, with its focus on engineering approaches to reducing occupational and community noise exposure. The organization and mission of this Program were documented shortly after its inception, and individual programmatic components have been the subject of subsequent papers. This paper summarizes the status and accomplishments of the engineering aspects of the Program from a five-year retrospective viewpoint and includes a review of retrofit noise control solution strategies, which have not been previously documented.

Cooper, Beth A.↗

Legacy Effects of Cropping System and Precipitation Influence the Core Camelina sativa Microbiome

Camelina ( Camelina sativa L.) is a potential biofuel crop and beneficial rotation crop in dryland cropping systems. Little is known about camelina microbiota or the legacy effect of soil origin/cropping system zones on camelina-associated microbiome assembly. To explore camelina-microbe associations, we grew camelina in the greenhouse using soil transplanted from 33 locations in the dryland wheat production area of eastern Washington. Bacterial, archaeal, and fungal communities from bulk soil, rhizosphere, and endosphere were characterized with 16S rRNA and internal transcribed spacer amplicon sequencing and were analyzed alongside site-specific climatic and edaphic data. We found that soil from the highest precipitation zone had higher alpha diversity than soil from the driest zone, but this effect was not seen in the greenhouse rhizosphere or endosphere. Plant compartment, cropping system zone, and soil origin all significantly influenced microbial composition, with soil pH and organic matter, as well as precipitation at origin, as major predictors. Analysis of abundance–occupancy distributions showed that the Actinobacteriota Aeromicrobium and Marmoricola and the fungus Pseudogymnoascus in the rhizosphere were plant-selected, while the endosphere was characterized by a number of Actinobacteriota, Rhizobium, and Clostridium. Sphingomonas amplicon sequence variants were also consistently enriched in the rhizosphere, suggesting that they are present in soils collected throughout eastern Washington and may represent good candidate biostimulants. Several lignin decomposing fungi had site-specific rhizospheric distributions, suggesting that they may be dispersal-limited or result from the legacy effect of long-term wheat cropping. Overall, this study contributes to our understanding of microbiome assembly in and on camelina roots while also highlighting the potential impact of cropping history on soil- and plant-associated microbiomes. [Formula: see text] The author(s) have dedicated the work to the public domain under the Creative Commons CC0 “No Rights Reserved” license by waiving all of his or her rights to the work worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law, 2025.

Barnes, Elle M↗

Binding profiles for 961 Drosophila and C. elegans transcription factors reveal tissue-specific regulatory relationships

A catalog of transcription factor (TF) binding sites in the genome is critical for deciphering regulatory relationships. Here, we present the culmination of the efforts of the modENCODE (model organism Encyclopedia of DNA Elements) and modERN (model organism Encyclopedia of Regulatory Networks) consortia to systematically assay TF binding events in vivo in two major model organisms,Drosophila melanogaster(fly) andCaenorhabditis elegans(worm). These data sets comprise 605 TFs identifying 3.6 M sites in the fly and 356 TFs identifying 0.9 M sites in the worm, and represent the majority of the regulatory space in each genome. We demonstrate that TFs associate with chromatin in clusters termed “metapeaks,” that larger metapeaks have characteristics of high-occupancy target (HOT) regions, and that the importance of consensus sequence motifs bound by TFs depends on metapeak size and complexity. Combining ChIP-seq data with single-cell RNA-seq data in a machine-learning model identifies TFs with a prominent role in promoting target gene expression in specific cell types, even differentiating between parent–daughter cells during embryogenesis. These data are a rich resource for the community that should fuel and guide future investigations into TF function. To facilitate data accessibility and utility, all strains expressing green fluorescent protein (GFP)-tagged TFs are available at the stock centers for each organism. The chromatin immunoprecipitation sequencing data are available through the ENCODE Data Coordinating Center, GEO, and through a direct interface that provides rapid access to processed data sets and summary analyses, as well as widgets to probe the cell-type-specific TF–target relationships.

Biochemistry & Molecular Biology↗

Hanford Site Bee Nest Box Monitoring Report for Calendar Year 2021

This report summarizes the results of the third year of monitoring bee nest boxes on the Hanford Site. Twenty bee nest boxes were installed as a component of compensatory mitigation for the installation of the L-894 water line between the 200-East and 200-West Areas of the Hanford Site in July 2019. The goal of this compensatory mitigation is to replace lost nesting habitat for above-ground nesting bees in a mature sagebrush ecosystem. Annual monitoring will track the condition and occupation of the bee nest boxes to determine if the compensatory mitigation was successful and to identify best practices when replacing nesting habitat for native bees.

54 ENVIRONMENTAL SCIENCES↗

Hanford Site Bee Nest Box Monitoring Report for Calendar Year 2020

This report summarizes the results of the second year of monitoring bee nest boxes on the Hanford Site. Twenty bee nest boxes were installed as a component of compensatory mitigation for the installation of the L-894 water line between the 200-East and 200-West Areas of the Hanford Site in July 2019. The goal of this compensatory mitigation is to replace lost nesting habitat for above-ground nesting bees in a mature sagebrush ecosystem. Annual monitoring will track the condition and occupation of the bee nest boxes to determine if the compensatory mitigation was successful and to identify best practices when replacing nesting habitat for native bees.

54 ENVIRONMENTAL SCIENCES↗

A simulation-based assessment of technologies to reduce heat emissions from buildings

Heat emissions from buildings are part of anthropogenic heat leading to urban overheating. This paper aims to assess how technologies (i.e., energy conservation measures - ECMs), used to decrease energy use, may also reduce heat emissions from buildings. This study employs the physics-based engine EnergyPlus to simulate the main components of heat emissions from buildings to ambient air: envelope, zone, and systems. Hourly simulations are run for IECC single- and multi-family reference models with three representative climates: Miami, Baltimore, and Chicago. The results show that the performance of ECMs varies among weather, seasons, and residential typologies. Particularly, some ECMs (i.e., cool coatings, heat pumps, additional insulation, energy-awareness occupants) show a strong decrease in heat emissions, yet they are not always correlated with proportional decreases in energy use. When all ECMs are combined, the reductions are larger on heat emissions (89%) than on site energy (65%) from the base cases. During summer in Miami, the combination of ECMs shows a decrease in heat emissions from the building surface component of 80% during daytime, 92% for the HVAC component and a counterbalanced increase in the zone component of 88%, bringing to a daily decrease in total heat emissions. The main contributions of this study are quantifying how typical ECMs influence residential building heat emissions using EnergyPlus simulations and informing urban planners and stakeholders on prioritizing measures for mitigating urban overheating problems.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

The Russian Invasion of Ukraine and Nuclear Security

You have in your hands a unique publication. Voices of Ukraine is a collection of testimonies from people working in the nuclear and radioactive source sector in Ukraine. The five texts in this extract are a preview of the full volume that will be published in early 2023. The accounts presented in this extract are very different from the newspaper articles or reports you may have read about the Russian invasion of Ukraine and the attack on and occupation of the Chornobyl Exclusion Zone and Zaporizhzhia NPP. Five people share their own stories of the personal and professional dilemmas they faced: How to endure an unending shift under enemy occupation when replacement workers weren’t permitted to relieve the staff; whether to remain in your childhood home or to flee abroad; how to support your community and country while maintaining the safe operation of nuclear sites in wartime conditions? The narratives of these individuals have far-reaching consequences for the nuclear sector in Ukraine but also far beyond it.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Motel solar hot-water installation--Atlanta, Georgia

Analysis of hardness of local water, average insolation for site, and daily hot water requirements insures suitability of solar-energy system design. Report describes two units which are designed to supply 81 percent of motel's annual hot water demand based on hypothetical 85 percent occupancy. Report includes drawings, operating and maintenance instructions, and test results for 1 day of operation.

Source record↗

Cationic Ordering and Its Influence on the Magnetic Properties of Co-Rich Cobalt Ferrite Thin Films Prepared by Reactive Solid Phase Epitaxy on Nb-Doped SrTiO 3 (001)

Here, we present the (element-specific) magnetic properties and cation ordering for ultrathin Co-rich cobalt ferrite films. Two Co-rich Co x Fe 3-x O 4 films with different stoichiometry (x=1.1 and x=1.4) have been formed by reactive solid phase epitaxy due to post-deposition annealing from epitaxial CoO/Fe 3 O 4 bilayers deposited before on Nb-doped SrTiO 3 (001). The electronic structure, stoichiometry and homogeneity of the cation distribution of the resulting cobalt ferrite films were verified by angle-resolved hard X-ray photoelectron spectroscopy. From X-ray magnetic circular dichroism measurements, the occupancies of the different sublattices were determined using charge-transfer multiplet calculations. For both ferrite films, a partially inverse spinel structure is found with increased amount of Co 3+ cations in the low-spin state on octahedral sites for the Co 1.4 Fe 1.6 O 4 film. These findings concur with the results obtained by superconducting quantum interference device measurements. Further, the latter measurements revealed the presence of an additional soft magnetic phase probably due to cobalt ferrite islands emerging from the surface, as suggested by atomic force microscope measurements.

36 MATERIALS SCIENCE↗

Orbital ordering in the layered perovskite material CsVF 4

In strongly correlated electronic systems, several novel physical properties are induced by the orbital degree of freedom. In particular, orbital degeneracy near the Fermi level leads to spontaneous symmetry breaking, such as the nematic state in FeSe and the orbital ordering in several perovskite systems. Here, the novel layered perovskite material CsVF 4 , with a 3 d 2 electronic configuration, was systematically studied using density-functional theory and a multiorbital Hubbard model within the Hatree-Fock approximation. Furthermore, our results show that CsVF 4 should be magnetic, with a G-type antiferromagnetic arrangement in the a b plane and weak antiferromagnetic exchange along the c axis, in agreement with experimental results. Driven by the Jahn-Teller distortion in the VF 6 octahedra that shorten the c axis, the system displays an interesting electron occupancy d x y 1 ( d x z d y z ) 1 corresponding to the lower nondegenerate d x y orbital being half-filled and the other two degenerate d y z and d x z orbitals sharing one electron per site. We show that this degeneracy is broken and a novel d y z / d x z staggered orbital pattern is here predicted by both the first-principles and Hubbard model calculations. This orbital ordering is driven by the electronic instability associated with degeneracy removal to lower the energy.

36 MATERIALS SCIENCE↗