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At least 55 records · Page 3

Predicting the Likelihood of Human-Elephant Conflict and Assessing Patterns in Elephant Movements Over Varying Habitat Conditions in the Kavango-Zambezi Area

In the Kavango-Zambezi area of southern Africa, three million people live within areas frequently traveled by free-ranging elephants. As the region continues to develop rapidly, urban and agricultural settlements further encroach upon the land that these elephants use. As elephants come into more frequent contact with urban and agricultural areas, human populations face financial loss through crop damage and the potential for injury from direct conflict with elephants. Elephant populations are also at risk of injuries from conflict as well as illness related to the consumption of waste. In order to implement human-elephant conflict mitigation strategies, local conservation groups need to be informed on best practices for coexistence. This project aided The Ecoexist Project and Connected Conservation in understanding the ecological factors that drive elephant movement into human settlements and provided Earth observation data to support conflict management in the future. The team used Landsat 5 Thematic Mapper (TM), Landsat 8 Operational Land Imager (OLI) data to create land use land cover maps and calculate vegetation indices, and used TerraClimate data to analyze drought conditions. These classified maps allowed us to display a time series of human settlement from 1990 to the present and were made explorable alongside other environmental variables in an updated Google Earth Engine (GEE) tool. This project also provided heat maps that show the risk of human-elephant conflict based on historical data of HEC locations. This analysis will provide support for conservation experts in determining best practices for future mitigation and prevention of human-elephant conflict.

Ariel Calle

Assessing Land Cover Change Dynamics in the Peruvian Amazon to Map Outbreak Risk and Inform Public Health Interventions for Zoonotic Disease Prevention

Dengue fever and leishmaniasis are two tropical diseases prevalent in Madre de Dios Region of Peru and have been associated with urbanization and road construction. Rapid land use changes such as mining, timber harvesting, and hydroelectric dam development lead to denser human presence in previously sparsely-populated areas which increases the proximity of human settlements to zoonotic disease vectors. In partnership with the Peruvian Ministries of Health (MINSA), the Environment (MINAM), and other in-country collaborators, a NASA DEVELOP team examined Land Use Land Cover (LULC) changes and reported dengue and leishmaniasis incidence in the Madre de Dios region. This sought to help MINSA and MINAM understand the spatial relationship between land use change and zoonotic disease incidence. We created a LULC classification script using Google Earth Engine (GEE) with Landsat 5 Thematic Mapper (TM) and Landsat 8 Operational Land Imager (OLI) imagery to classify land cover in 2010, 2015, and 2020 and evaluate changes over this time period. The team then compared the quantified results of the LULC assessment in conjunction with reported disease cases to evaluate disease incidence and key land cover changes across Madre de Dios’s 11 districts. Follow on work will use these products to develop more detailed outbreak risk maps. These products will allow MINSA, MINAM, and other partners to understand hotspots of land cover change in Peru and the relationship with outbreaks to inform public health decision makers and environmental policy.

Nataly Chacon-Buitrago

Central America Disasters: Using Earth Observations to Map Flooding for Disaster Monitoring, Inform Potential Risk, and Prepare for Possible Response

In November 2020, Hurricanes Eta and Iota hit Central America within weeks of each other, causing severe flooding, landslides, and widespread damage. NASA DEVELOP partnered with Comité Regional de Recursos Hidráulicos (CRRH), Centro de Coordinación para la Prevención de los Desastres en América Central y República Dominicana (CEPREDENAC), and Sistema de la Integración Centroamericana (SICA) to better understand how flooding throughout Central America has impacted and will continue to affect communities, focusing on sites in Guatemala, Honduras, El Salvador, Belize, Nicaragua, western Panama, and eastern Costa Rica from January 2015 to October 2021. The team utilized surface reflectance data from Landsat 7 Enhanced Thematic Mapper Plus (ETM+), Landsat 8 Operational Land Imager (OLI), Sentinel-2 MultiSpectral Instrument (MSI), Suomi National Polar-orbiting Partnership (NPP) Visible Infrared Imaging Radiometer Suite (VIIRS), and Terra Moderate Resolution Imaging Spectroradiometer (MODIS). This project also utilized backscatter data from Sentinel-1 C-band Synthetic Aperture Radar (C-SAR) and elevation data from the Shuttle Radar Topography Mission (SRTM). Incorporating these Earth observations in NASA SERVIR’s Hydrologic Remote Sensing Analysis for Floods (HYDRAFloods) tool run on Google Earth Engine (GEE), the team produced historical surface water maps, a case study analysis of the two hurricanes, and a code tutorial. These results indicated that surface water increased in priority sites from 2015 to 2021, optical and SAR imagery detected similar flood patterns and extent after the hurricanes, and rainfall was concentrated on the east coast of the region. These products allow partners to make informed decisions around flooding preparation and disaster mitigation.

Caroline Williams

Black Hills Wildfires: Mapping Post-fire Conifer Regeneration using Snow-on Imagery

The 2000 Jasper Fire in the Black Hills of South Dakota was the largest wildfire to date in the region, burning over 83,000 acres of ponderosa pine forest. In collaboration with partners from the United States Forest Service (USFS) Black Hills Experimental Forest, USFS Rocky Mountain Research Station, and United States Geological Survey Geosciences and Environmental Change Science Center, we characterized post-fire forest regeneration within high-severity burn patches. We accomplished this by implementing novel conifer detection techniques using a snow index mask to create a winter, snow-on image composite from Landsat 8 Operational Land Imager (OLI) and Sentinel-2 Multispectral Instrument (MSI) data. We utilized 2015 USFS stem maps of field-observed regeneration plots and ocularly sampled additional reforestation sites planted in 2001–2013. In Google Earth Engine (GEE), the field data and imagery were used to train a Random Forest (RF) model. The RF model classified 2021 conifer regeneration density as low, medium, or high across the high-severity burn area with an overall accuracy of 81.3%. Approximately 45.9% of the high-severity burn had low or no regeneration (0-40 trees per acre) 20 years post-fire. Given our partners' desire to find easily accessible low conifer regeneration zones, we identified 4,079 acres of priority planting sites that were within 1,500 feet of roads, had not been planted previously, and were larger than 50 acres. This method supports the use of snow-on imagery as a successful technique to identify conifer regeneration.

Casey Menick​

Black Hills Wildfires: Mapping Post-Fire Conifer Regeneration using Snow-On Imagery

The 2000 Jasper Fire in the Black Hills of South Dakota was the largest wildfire to date in the region, burning over 83,000 acres of ponderosa pine forest. In collaboration with partners from the United States Forest Service (USFS) Black Hills Experimental Forest, USFS Rocky Mountain Research Station, and United States Geological Survey Geosciences and Environmental Change Science Center, we characterized post-fire forest regeneration within high-severity burn patches. We accomplished this by implementing novel conifer detection techniques using a snow index mask to create a winter, snow-on image composite from Landsat 8 Operational Land Imager (OLI) and Sentinel-2 Multispectral Instrument (MSI) data. We utilized 2015 USFS stem maps of field-observed regeneration plots and ocularly sampled additional reforestation sites planted in 2001–2013. In Google Earth Engine (GEE), the field data and imagery were used to train a Random Forest (RF) model. The RF model classified 2021 conifer regeneration density as low, medium, or high across the high-severity burn area with an overall accuracy of 81.3%. Approximately 45.9% of the high-severity burn had low or no regeneration (0-40 trees per acre) 20 years post-fire. Given our partners' desire to find easily accessible low conifer regeneration zones, we identified 4,079 acres of priority planting sites that were within 1,500 feet of roads, had not been planted previously, and were larger than 50 acres. This method supports the use of snow-on imagery as a successful technique to identify conifer regeneration.

Casey Menick

Maldives Climate: Monitoring Shoreline Changes and Island Loss in Response to Climate Change

Global sea level rise as a result of climate change continues to pose a critical threat to coastal ecosystems and populations. The archipelagic country of the Maldives is of critical concern due to being one of the lowest lying areas in the world. The development of reclaimed land in the Maldives by sand dredging has been a frequent response to both increasing sea levels and population increase. Such disturbance can lead to increased sedimentation off the coast and negatively impact coastal environments. Remote sensing tools such as satellite imagery have proved to be an effective tool in observing coastal changes in response to climate change and development. NASA DEVELOP created a methodology to analyze both water quality and shoreline erosion in the Maldives utilizing satellite imagery. Methods relied on open-source software such as QGIS and Google Earth Engine (GEE) and Satellite Imagery from PlanetScope, Landsat 8 Operational Land Instrument (OLI), Sentinel-2 Multi Spectral Instrument (MSI), and Aqua & Terra Moderate Resolution Imaging Radiospectrometer (MODIS) to analyze the changes in shorelines and assess water quality of select atolls within the Maldives. Findings show less shoreline change in developed parts of the island and more shoreline change in natural parts of the island. Additionally, water quality varies throughout the year and our data did not indicate seasonal trends. The methodology will be replicated to continue to monitor island erosion and water quality with the Maldives and will be applicable to other island and coastal systems.

remote sensing

Southern Idaho Ecological Conservation: Investigating the Impact of Targeted Grazing to Improve Wetland Habitat in the Sterling Wildlife Management Area

Wetland ecosystems are vital for biodiversity conservation and ecosystem services. The Sterling Wildlife Management Area in Bingham County, Idaho, has management concerns about decadent and accumulated vegetation growth encroaching on wetland habitat, which presents challenges for wildlife, decreases biodiversity, and limits public access. Targeted grazing has been proposed as a sustainable alternative to chemical herbicides or burning. Land managers introduced targeted cattle grazing in January 2021 to reduce biomass. NASA DEVELOP partnered with the Idaho Department of Fish and Game to determine the impact of grazing using NASA Earth observations from Landsat 8 Operational Land Imager (OLI) in Google Earth Engine (GEE). Images were processed with TerrSet’s Land Change Modeler and ArcGIS Pro’s Change Detection Wizard to understand land changes following grazing. A Normalized Difference Vegetation Index (NDVI) analysis was performed to assess impacts on vegetation productivity and compare variance in biomass before and after grazing. A Normalized Difference Water Index (NDWI) was used to compare changes in the wetland and its vegetation content to evaluate the suitability of the area for migratory birds post-grazing. Results showed a decrease in the vegetation index and an increase in the water index postgrazing. The DEVELOP team’s analysis suggests that grazing helps break down thick, senesced vegetation and increase soil moisture. Providing a workflow model will aid partners in continuing to monitor this management area and other management areas across the state.

change detection

Bhutan Agriculture III: Monitoring Cropland Changes in Bhutan using Remote Sensing to Bolster Food Security and Support Crop Monitoring

The Bhutan Agriculture III team aimed to improve agricultural efficiency in Bhutan. Bhutan is a nation heavily reliant on agriculture, but it faces challenges such as geophysical limitations and lack of scientific agricultural practice. The team partnered with a primary end user, Bhutan’s Department of Agriculture (DoA), and with collaborators; the Bhutan Foundation, National Plant Protection Centre (NPPC), Agricultural Research Department Centre (ARDC), National Statistics Bureau (NSB), and the Ugyen Wangchuck Institute for Conservation and Environment Research (UWICER). Advised by NASA SERVIR, the team developed crop masks and monitored rice distribution from 2015 to 2022 utilizing Earth observations such as Landsat 8 Operational Land Imager (OLI), Landsat 9 OLI-2, Sentinel-1 C-Band Synthetic Aperture Radar (C-SAR), Sentinel-2 MultiSpectral Instrument (MSI) and Shuttle Radar Topography Mission (SRTM). The team gathered 5,000 points from the five dzongkhags that yield the most rice in Bhutan (Paro, Punakha, Samtse, Sarpang and Wangue Phodrang) using Collect Earth Online (CEO). With the data collected, the team split the data into training and validation data on Google Earth Engine (GEE) for a random forest (RF) classifier for rice and non-rice classification. After running the data on the Random Forest (RF) model, the team got an accuracy score of 81.48%, a kappa score of 55.75% and an F1 score of 86.11%. This data supports better agricultural decision-making for the governing body of Bhutan, helps enhance farming efficiency and foster sustainable practices, assists in overcoming data inaccuracy and bolsters food security in the country.

Sonam Seldon Tshering

Muon g-2 Experiment

The Muon g-2 experiment probes the magnetic properties of the muon—a heavy sibling of the electron—in the search for new physics. Muon g-2 (pronounced gee-minus-two) is an international collaboration between Fermilab and dozens of labs and universities in seven countries. The Muon g-2 experiment studies the precession or “wobble” of muons when placed in a magnetic field. Based on what we already know about muons and other particles, scientists can predict with great precision the value of the muons’ wobble. If the experiment comes up with something different, it means that our current understanding of physics is incomplete, and it may indicate the presence of additional particles or hidden subatomic forces. It would open the door to exciting new realms of science.

Fermilab, Fermilab

Water‐mediated Decomposition Pathways of ε‐Hexanitrohexaazaisowurtzitane

The dominant initial decomposition mechanism of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (HNIW) is understood from the literature to be the N─NO 2 bond scission unimolecular mechanism. Here we have found a water-mediated HONO release initial decomposition mechanism energetically competitive with the N─NO 2 bond scission mechanism modeled using ab initio nudged elastic band simulations. The activation energy of the water-mediated HONO mechanism was calculated to be 138.9 kJ/mol with the Perdew, Burke, and Ernzerhof (PBE) functional (177.8 with PBE0), while the double NO 2 release mechanism is 171.9 kJ/mol (203.3 with PBE0). Branching secondary, tertiary, and quaternary decomposition steps were also discovered including oxidation of HONO or H 2 O causing ring-opening that leads to C─N bond breaking and N 2 O or NO release. The reaction rate of HONO oxidation is much faster than HONO release, making the HONO concentration low. The Helmholtz free energy barrier of the double NO 2 release mechanism is lower than the water-mediated HONO release above 438 K (165°C) due to the vibrational contribution to the free energy. This helps explain why the literature reports more NO 2 release at higher temperatures. The present study reveals a physical mechanism for how water can catalyze the decomposition of HNIW at low enough temperatures, and reveals secondary, tertiary, and quaternary reaction mechanisms leading to NO x release. In conclusion, as water is realistically always present, the reported barriers are important for building kinetic models needed to ensure the safety and reliability of HNIW.

Steele, Brad A. [Lawrence Livermore National Labor

Data‐Efficient Generation of Synthetic Microstructures of Polymer‐Bonded Energetic Material With Fine‐Tuned Stable Diffusion

Among current deep learning approaches for synthetic image generation, diffusion-based models stand out in terms of algorithmic stability and ability to retain high-fidelity image features with detailed resolution. Here, in this work, we employ Dreambooth, a method for fine-tuning Stable Diffusion, on X-ray CT images of microstructure of the polymer-bonded form (PBX) of a commonly used high explosive, Pentaerythritol tetranitrate (PETN), which yields generative models for creating synthetic PBX images. The models developed here represent five classes (or ‘lots’) of microstructures and demonstrate successful generation of images of each class with high fidelity, as verified by computed classification accuracy of ∼ 94% or higher. Data augmentation afforded by such image synthesis can be used to more reliably decipher underlying statistics, build processing-structure correlations, recognize off-normal structural anomalies, and identify age-related changes. Ideas related to converting image data into appropriate density mapping and performing mesoscale simulation or surrogate modeling of detonation are also discussed.

Dreambooth

Improvement of Drop‐Hammer Impact Testing for Safety Assessment of High Explosives Using 10‐mg Samples

Here, in this study, we established an improved method for drop-hammer impact testing of small quantities of high explosives (10 mg). We performed about seven hundred impact tests under various experimental conditions (e.g., sandpaper vs bare anvil, different sample masses, drop-weights, and striker diameters) to determine an optimal set of conditions and reaction detection methods (e.g., gas analysis, video, and sound recordings) that give the most statistically reliable results with 10 mg samples. We used both Frequentist and Bayesian statistical approaches to compare estimates of the drop height (DH50) that initiates a reaction 50% of the time, and to quantify the associated uncertainty. Gas analysis proved to be the most reliable reaction detection method, showing unambiguous rises in HE decomposition products (e.g., CO 2 ) even when the other indicators (e.g., sound, video) were inconclusive. The impact tests performed with a bare anvil showed much better reproducibility than those conducted with sandpaper, reducing the largest uncertainty observed in the data sets by a factor of 1.7. The DH 50 values obtained from three different sample masses (10, 20, and 35 mg) fell within the uncertainties of the measurements. We demonstrated the improved procedure (i.e., 10-mg samples, gas analysis, bare anvil, and Bayesian approach) on a variety of PETN samples having different surface areas and thermal histories.

PETN

Ligand‐induced CaMKIIα hub Trp403 flip, hub domain stacking, and modulation of kinase activity

Abstract γ‐Hydroxybutyric acid (GHB) analogs are small molecules that bind competitively to a specific cavity in the oligomeric CaMKIIα hub domain. Binding affects conformation and stability of the hub domain, which may explain the neuroprotective action of some of these compounds. Here, we describe molecular details of interaction of the larger‐type GHB analog 2‐(6‐(4‐chlorophenyl)imidazo[1,2‐b]pyridazine‐2‐yl)acetic acid (PIPA). Like smaller‐type analogs, PIPA binding to the CaMKIIα hub domain promoted thermal stability. PIPA additionally modulated CaMKIIα activity under sub‐maximal CaM concentrations and ultimately led to reduced substrate phosphorylation. A high‐resolution X‐ray crystal structure of a stabilized CaMKIIα (6x mutant) hub construct revealed details of the binding mode of PIPA, which involved outward placement of tryptophan 403 (Trp403), a central residue in a flexible loop close to the upper hub cavity. Small‐angle X‐ray scattering (SAXS) solution structures and mass photometry of the CaMKIIα wild‐type hub domain in the presence of PIPA revealed a high degree of ordered self‐association (stacks of CaMKIIα hub domains). This stacking neither occurred with the smaller compound 3‐hydroxycyclopent‐1‐enecarboxylic acid (HOCPCA), nor when Trp403 was replaced with leucine (W403L). Additionally, CaMKIIα W403L hub was stabilized to a larger extent by PIPA compared to CaMKIIα hub wild type, indicating that loop flexibility is important for holoenzyme stability. Thus, we propose that ligand‐induced outward placement of Trp403 by PIPA, which promotes an unforeseen mechanism of hub domain stacking, may be involved in the observed reduction in CaMKIIα kinase activity. Altogether, this sheds new light on allosteric regulation of CaMKIIα activity via the hub domain.

Biochemistry & Molecular Biology

Carbon monoxide chemistry of α-V70I Mo-nitrogenase: Evidence from EPR- and IR-monitored photolysis – or, what a difference a methyl makes

A critical step in the global nitrogen cycle is the conversion of dinitrogen into biologically accessible ammonia. In Nature this is accomplished by the nitrogenase (N 2 ase) family of enzymes. Carbon monoxide (CO) has long been known as an inhibitor of dinitrogen reduction by N 2 ase, but it can also be a substrate of the enzyme, when it is catalytically reduced to hydrocarbons. Understanding the CO interactions with N 2 ases are thus relevant to both dinitrogen fixation and Fischer-Tropsch-like chemistry. Here, in this work, the interaction of CO with the α-V70I variant of Azotobacter vinelandii MoFe N 2 ase was investigated using electron paramagnetic resonance (EPR) and infrared (IR) monitored photolysis of bound CO under cryogenic conditions. This was supplemented by further analysis of stopped-flow Fourier transform IR (SF-FT-IR) data under turnover conditions. The α-V70I variant adds a single methyl group close to the FeMo-cofactor active site, and the results show that this inhibits and slows, but does not substantially chemically change, the binding of CO to the FeMocofactor. The EPR spectra of both the hi-CO and lo-CO states closely resemble those from the wild-type enzyme. Similarly, the SF-FT-IR spectra of CO inhibited α-V70I and wild-type enzyme are strikingly similar, showing only small shifts in band energies which allow better interpretation of the published wild-type spectra. The extra carbon does, however, impact and inhibit the photochemical release and migration of CO at cryogenic temperatures, resulting in novel CO-bound species. These include a product species, termed Lo-1*, which may involve CO photochemically migrating on the FeMo-cofactor.

Carbon monoxide

Reactive oxygen species control protein degradation at the mitochondrial import gate

While reactive oxygen species (ROS) have long been known to drive aging and neurodegeneration, their persistent depletion below basal levels also disrupts organismal function. Cells counteract loss of basal ROS via the reductive stress response, but the identity and biochemical activity of ROS sensed by this pathway remain unknown. Here, we show that the central enzyme of the reductive stress response, the E3 ligase Cullin 2-FEM1 homolog B (CUL2 FEM1B ), specifically acts at mitochondrial TOM complexes, where it senses ROS produced by complex III of the electron transport chain (ETC). ROS depletion during times of low ETC activity triggers the localized degradation of CUL2 FEM1B substrates, which sustains mitochondrial import and ensures the biogenesis of the rate-limiting ETC complex IV. As complex III yields most ROS when the ETC outpaces metabolic demands or oxygen availability, basal ROS are sentinels of mitochondrial activity that help cells adjust their ETC to changing environments, as required for cell differentiation and survival.

FEM1B

Hygrothermal aging effects on polyimide and acrylate-based adhesive materials in high-performance flat-flex cable assemblies

Flat-flex assemblies are widely used across a diverse range of technologies, including consumer electronics, automotive systems, aerospace and defense applications, and medical devices, due to their compact form factor and flexibility. However, environmental stressors like temperature and humidity are known to degrade performance over time, though the main mechanisms for degradation remain unknown. Here, in this work, we examined the aging behavior of copper/polyimide/adhesive laminate systems under varying temperature and humidity conditions, focusing on material degradation and its effects on mechanical and dielectric properties. Results show that peel strength and breakdown voltage decrease with exposure time, temperature, and humidity; spectroscopic characterization revealed that the adhesive, and not the polyimide, is the weak link in the material stack-up. The adhesive, identified as a butyl acrylate-acrylonitrile (BA-AN) copolymer, exhibited age-related spectral changes that correlated with exposure severity and duration. Hydrolysis at BA ester and AN nitrile groups was identified as the primary degradation mechanism, producing amides, acids, and alcohols. We developed a mechanistic model that connects kinetic parameters for BA-AN spectral band decay to peel strength and breakdown voltage, and implicates hydrolysis at the AN moiety, not BA, in performance decrements. Modeling predictions at ambient conditions indicate faster decline in peel strength than dielectric strength at early times, followed by plateauing of both properties at longer times. These findings provide critical insights into laminate aging mechanisms and highlight the importance of addressing BA-AN degradation to improve the long-term reliability of these systems in high-humidity environments.

organic

Design Principles in Engineering of Multigrain Nanocatalysts via Multiscale Electronic Structure Characterization

Engineering grain boundary (GB) strain provides a promising pathway to tune the catalytic properties of nanocrystals. However, structural heterogeneity from random grain orientation and geometry has limited clear structure–property correlations. Here, we utilize a multigrain Co3O4/Mn3O4 core/shell nanocrystal platform as a model system to systematically investigate how geometric misfit strain at GBs serves as catalytically active sites for the oxygen reduction reaction. Through precise subnanometer-level control over grain morphology and by integrating multiscale electronic structure characterization, we identify the electronic structural signature of GB defects and establish a direct correlation between localized strain fields and modified electronic states. Strain modulation at GBs alters the eg orbital energy levels, with elongation along the z-axis combined with shear strain stabilizing the eg states, in contrast to the destabilization observed under pure shear strain. This stabilization mechanism enhances the electrocatalytic activity and selectivity of strained GBs compared with strain-relaxed grain surfaces. Furthermore, we reveal that GBs exhibit a radial strain gradient, producing a spatial energy shift that further modulates local electronic structures, as resolved through the classification of electron energy loss spectroscopy data. Together, these findings demonstrate that geometric misfit strain enables precise tuning of grain geometry and the resulting electronic structures, offering a robust strategy for engineering next-generation nanocatalysts.

Cho, Min Gee

How Does Metal Spin State Affect Electronic Communication in Mixed-Valence Dimers? Insights from Ultrafast Near-Infrared and Soft X-ray Transient Absorption Spectroscopy

Recent advancements in photocatalysis, photovoltaics, and quantum information science take advantage of electron spin, and determining how spin multiplicity affects electron transfer is key to understanding these phenomena. Here, in this study, we examine how metal spin state affects electronic communication in an organometallic mixed-valence dimer, ferrocenyl cobaltocenium ([Fe II Cp 2 Co III Cp 2 ] + ). This complex can be photoexcited from its low-spin singlet Fe II ground state to form intermediate-spin triplet Fe II and high-spin quintet Fe II excited states. Using femtosecond optical transient absorption (OTA) spectroscopy with visible (vis), near-infrared (NIR), and short-wave IR (SWIR) probes, supported by time-dependent density functional theory (TD-DFT) calculations, we measure Fe II Co III →Fe III Co II intervalence charge transfer (IVCT) bands in each of the Fe II spin states. Mulliken–Hush analysis of the excited-state IVCT bands was used to compute the electronic coupling between the metal centers in all three spin states, which increased as quintet < triplet < singlet. Meanwhile, the peak energy of the bands, and thus the ΔG of the IVCT transition, increased as triplet < quintet < singlet. Then, to directly probe the electronic structure at each metal center, we employed picosecond soft X-ray transient absorption (XTA) spectroscopy at the Fe and Co L 3 edges. Our results show that the low-spin and high-spin states of [Fe II Cp 2 Co III Cp 2 ] + are valence-localized, while the intermediate-spin state is partially delocalized. The differences in charge delocalization are attributed to differences in orbital occupation and geometry that affect the free energy and superexchange coupling.

Burke, John H. [Univ. of Illinois at Urbana-Champa