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All sourcesNASA NTRSDOE OSTI
NASA NTRSDate not supplied

Localizing Earth Science: The NASA DEVELOP Model of Community Science & Engagement

NASA’s DEVELOP Program conducts rapid feasibility studies that apply Earth observations to address community priorities and needs and enable informed decision making. Part of NASA’s Applied Sciences’ Capacity Building Program, DEVELOP builds skills in both participants (students, recent graduates, and early/transitioning career professionals) who conduct projects on small teams, and partner organizations (state and local governments, federal agencies, non-profit and for-profit organizations, and international organizations) that work closely with DEVELOP to design the project. While only a subset of DEVELOP partner organizations are local municipalities or community-led non-profits, the DEVELOP model is an effective engagement tool and often used by NASA as an introduction for communities to engage in Earth science research and familiarization with satellite remote sensing. This presentation will highlight the DEVELOP model of co-production and community collaboration, lessons learned in partnering with local communities, and evaluation activities that look at the program’s reach and efforts.

Robert Cecil Byles↗
DOE OSTI2025

Atomic Structure, Dynamics, Changes in Chemical Bonding and Semiconductor-Metal Transition in Sb 2 Se 3 : A Remarkable Material for Quantum Networks and Energy Applications

Antimony sesquiselenide has become an outstanding functional material for photovoltaics, energy storage and transformation, memory and photonic applications. Sb 2 Se 3 is one of the most successful emerging solar light absorbers and has also been identified as a highly promising ultralow-loss phase-change material (PCM) for next-generation coherent nanophotonic processors, photonic tensor cores, quantum and neuromorphic networks. Unlike benchmark telluride PCMs, Sb 2 Se 3 features a quasi-one-dimensional (1D) crystalline structure consisting of (Sb 4 Se 6 ) ∞ ribbons, lacks the typical PCM chemical bonding, and undergoes an extended semiconductor-metal transition above the melting point. Consequently, the origin of high optical contrast between crystalline (SET) and amorphous (RESET) logic states remains elusive and presents a significant challenge. Using high-energy X-ray diffraction and Raman spectroscopy over a wide temperature range, supported by first-principles simulations and complemented by thermal, optical and electrical measurements, as well as by 121 Sb-Mossbauer spectroscopy, the quasi-1D network of orthorhombic antimony sesquiselenide was found to undergo significant evolution in amorphous and supercooled Sb 2 Se 3 , leading to lower coordination, shorter interatomic distances and a higher p-electron density on antimony, indicating changes in chemical bonding. The observed novel Sb 2 Se 3 nanocrystalline polymorph, characterized by trigonal antimony coordination and more isolated Sb-Se ribbons, could help reduce multiple trapping defect states in the bandgap, which are typical of orthorhombic Sb 2 Se 3 , thereby enhancing the power-conversion efficiency of photovoltaic devices. Semimetallic and metallic liquid Sb 2 Se 3 exhibit a gradual transformation into a denser 2D and/or 3D network with higher antimony coordination. Localized electron states in the pseudogap are becoming extended, leading to an increase in electronic conductivity σ following the relationship σ ∝ N(E F ) 2 . Liquid Sb 2 Se 3 also appears to be strongly fragile, with a nonmonotonic change in viscosity and higher atomic mobility in the metallic liquid. Furthermore, these results explain extraordinary functionalities of Sb 2 Se 3 for photonic and energy applications.

antimony↗
DOE OSTI2025

Indoor Air Quality (IAQ) Monitoring for Space Farming Institute [Slides]

Through the U.S. Department of Energy's Energy to Communities (E2C) program, NREL, other national laboratory experts, and select organizations provide Expert Match - free, short-term technical assistance to address near-term energy challenges and questions. Expert Match is for community stakeholders who have decision-making power or influence in their community but need access to additional energy expertise to inform key upcoming decisions. This Expert Match request supported the Space Farming Institute, a nonprofit organization located in Anchorage, AK, with an indoor air quality analysis. The NREL team analyzed indoor air quality data provided by the Space Farming Institute, which experts at PNNL used to design an indoor bioreactor to grow Ulva algae for indoor air quality mitigation purposes.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2024

The United States' (DOE) Action Plan for Power Sector Decarbonization

A collaborative report from the Clean Energy Ministerial (CEM) on Lessons Learned for Rapid Decarbonization of Power Sectors was delivered to energy ministers and presented at the 13th CEM (CEM13) in the United States in September 2022. In light of these lessons learned and discussed at CEM13, several jurisdictions signaled intent to develop Action Plans for power sector decarbonization. The first cohort of Action Plans was released at CEM14 in India in July 2023. The U.S. Department of Energy (DOE) is pleased to release this Action Plan as a contribution to the second cohort of Action Plans released at CEM15 in Brazil in October 2024. The Action Plans, supported by the 21st Century Power Partnership, and other CEM workstreams via direct technical assistance and capacity building, are intended to focus on select implementation actions, given each country's existing power sector goals and activities, and are an opportunity for countries to display leadership in power sector decarbonization. The Action Plans are organized in a framework for Planning, Building and Operating, as well as Stakeholder Engagement where appropriate based on country priorities. These Action Plans are voluntary, developed by each country individually, not comprehensive of all activities within the jurisdiction, and are living documents that are subject to change. This Action Plan, developed by DOE, is focused on federal actions for power sector decarbonization primarily led by DOE. There are many other actions being led by other U.S. government agencies, or at the state and local level, that are not featured in this Action Plan.

21st Century Power Partnership↗
NASA NTRS1990

Ground states of partially connected binary neural networks

Neural networks defined by outer products of vectors over (-1, 0, 1) are considered. Patterns over (-1, 0, 1) define by their outer products partially connected neural networks consisting of internally strongly connected, externally weakly connected subnetworks. Subpatterns over (-1, 1) define subnetworks, and their combinations that agree in the common bits define permissible words. It is shown that the permissible words are locally stable states of the network, provided that each of the subnetworks stores mutually orthogonal subwords, or, at most, two subwords. It is also shown that when each of the subnetworks stores two mutually orthogonal binary subwords at most, the permissible words, defined as the combinations of the subwords (one corresponding to each subnetwork), that agree in their common bits are the unique ground states of the associated energy function.

Baram, Yoram↗
DOE OSTI2026

FERC order 2222 & DER policy and implementation report - January 2026

The January 2026 FERC 2222 Tracker Report provides an overview of the progress and challenges in the implementation of FERC Order 2222, emphasizing the critical need for state-level action to address gaps in DERA/EDC communication protocols. The report highlights the importance of reliable communication between electric distribution companies (EDCs) and DER aggregators (DERAs) for seamless market operations, noting the absence of specific directives from FERC and RTO/ISO compliance filings. Key discussions include the operational coordination required to manage DER operations within aggregated markets, the potential use of tools like DER Registries for efficient data exchange, and the implications of non-performance due to communication issues. While steps are being taken at the state level, such as ongoing policy development and bi-monthly webinars for stakeholder education, no states have fully developed coordination frameworks as of early 2026. The report underscores the growing role of states and local regulators in defining these protocols and ensuring effective coordination amidst the complex dynamics of distributed energy resources (DERs) integration into wholesale markets.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2024

Controlling reversible phase transitions in rare-earth nickelates for novel memory devices

Resistive switching in correlated complex oxides is lucrative for emerging applications in neuromorphic computing, and densely scaled non-volatile memory. Electrical conductance of such complex oxides can be controllable switched across multiple orders of magnitude by either (a) electroforming a conduction channel (e.g., in tungsten oxide), or (b) inducing Mott-Hubbard transition (e.g., in rare-earth nickelates)– both via controlled migration of defects (such as oxygen vacancies) under applied bias. Nevertheless, the promise of such defect-driven electronic transitions are far from realized due to a lack of fundamental understanding of the atomic-scale processes that underlie migration and spatiotemporal evolution of oxygen vacancies over nano-to-mesoscopic length/timescales under applied electric field. In this project, we employ a synergistic integration of density functional theory (DFT) calculations, ab initio/classical molecular dynamics (AIMD/CMD) simulations, machine learning (ML), precision synthesis, and multi-modal X-ray imaging experiments to address this knowledge gap. Such an integrated approach offers to elucidate the correlations between subtle structural distortion and oxidation states; treat localized charge carriers; describe defect/ion transport in the presence of electric field; and, in turn, greatly advance the current understanding of microstructural evolution in complex oxides under applied bias. The fundamental knowledge gained from this work will enable precise control over hierarchical defect structures and unravel new routes to manipulate resistance states in complex oxides. This, in turn, will accelerate design of novel devices with desired set of neural functionalities, and high-speed densely-scaled resistive random access memory technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2026

1995 San Diego Region Travel Behavior Survey

The 1995 San Diego Region Travel Behavior Survey was conducted January-June of 1995 under the auspices of the San Diego Association of Governments. The survey was an essential element in the regional study of transportation activity and travel patterns. The survey was designed to examine the relationship between characteristics of households and travel behavior, as well as to provide information state and local decision makers require when considering future regional transportation needs and investments. In total, 2,375 households were recruited to participate in the study. Of these, 2,062 households completed travel diaries, and the information was retrieved from all household members older than age five. 2,049 were successfully geocoded to California state plane coordinates for home addresses. A total of 17,060 trips were profiled in the course of this survey during the assigned 24-hour weekday.

1Hz data↗
NASA NTRSDate not supplied

NASA DEVELOP’s Approach to Co-Production and Collaborative STEM Engagement

The NASA DEVELOP Program conducts 50-60 projects each year with the goal of bringing the benefits of NASA Earth science to local decision-making challenges. DEVELOP, part of NASA’s Applied Sciences’ Capacity Building Program, connects end users with students, recent graduates, and early and transitioning career professionals through 10-week rapid feasibility studies. These projects are a collaboration between NASA, DEVELOP office host locations (universities and other federal installations), project partners (federal agencies, state and local governments, non-profit and for-profit organizations, and international organizations), and the project teams who conduct them. The projects take place under the guidance of science advisors from NASA, academia, and partner organizations, and introduces communities to new applications of NASA Earth observations data with the desired outcome of informed decision-making. This presentation will highlight the DEVELOP model of co-production and programmatic collaboration, lessons learned in partnering, and evaluation activities that look at the impact of the program’s efforts.

Capacity Building↗
DOE OSTI2025

Threat Hunt Guide for BESS Environments

The rapid digitalization of the electric grid - driven by the integration of inverter-based resources (IBRs), battery energy storage systems (BESS), and advanced grid control platforms - has significantly enhanced grid efficiency, visibility, and flexibility. However, this evolution also introduces new cybersecurity risks, particularly through supply chain dependencies and operational blind spots at the grid edge. To address these challenges, Idaho National Laboratory (INL), through the Department of Energy (DOE) Office of Cybersecurity, Energy Security, and Emergency Response (CESER) Rapid Risk initiative, conducted a series of rapid risk assessment engagements with energy organizations across the United States. Drawing on lessons learned from these engagements, INL developed the following threat hunting guide for asset owners and operators (AOOs) to enhance their cybersecurity visibility within BESS and IBR systems. The guide demonstrates how to use passive network monitoring to baseline device behavior, detect adversarial activity, and investigate anomalies without disrupting operations. By implementing these practices, energy sector stakeholders can improve coordination between cybersecurity and operations teams and strengthen the resilience of distributed energy resources (DERs) within the modern power grid. Prior to implementing any network monitoring, packet capture, or threat hunting activity described in this guide, AOOs are strongly advised to review applicable governance frameworks, legal requirements, and organizational policies. This guide is intended for informational and educational purposes only. It does not replace compliance with any federal, state, or local cybersecurity mandates or industry standards. Implementation of described configurations, technologies, or analytic workflows is performed at the discretion and responsibility of the asset owner and operator.

25 - ENERGY STORAGE↗
DOE OSTI2026

Bridging Transition Metal and Anion Redox Processes in Li-Rich Sulfide Cathodes

Li-ion batteries are essential for decarbonizing global transport and energy, but their scalability is constrained by limited supplies of critical cathode elements, such as Ni, Mn, Co, and P. To address this, we previously introduced high-energydensity Li-ion cathodes composed of Al, Fe, and S, which are elements already produced globally at industrial scale and batterygrade purity. These cathodes leverage sulfide anion redox, involving nonbonding S 3p states and localized distortions that form and break S−S bonds, enabling high capacity. Here, we expand this chemical space by incorporating Cu into cathodes Li 2.2d−z Cu z Al 0.2 Fe 0.6 S 2 (0 ≤ z ≤ 0.4), where highly covalent Cu−S interactions stabilize holes on Cu as Cu >1+ . This Cu redox extends charge compensation that was previously restricted to localized, electronically isolated S−S bonds. Cu also limits capacity, which we attribute to structural destabilization of the delithiated phase, despite the thermodynamic stability of Cu >1+ . By describing the effects of Cu on charge compensation and phase stability, we present a sulfide anion redox mechanism for next-generation multielectron redox Li-ion cathodes, where highly covalent transition metal states participate in otherwise electronically isolated redox processes involving anion nonbonding states.

Anions↗
NASA NTRS1983

Assessment of institutional barriers to the use of natural gas fuel in automotive vehicle fleets

Institutional barriers to the use of natural gas as a fuel for motor vehicle fleets were identified. Recommendations for barrier removal were developed. Eight types of institutional barriers were assessed: (1) lack of a national standard for the safe design and certification of natural gas vehicles and refueling stations; (2) excessively conservative or misapplied state and local regulations, including bridge and tunnel restrictions, restrictions on types of vehicles that may be fueled by natural gas, zoning regulations that prohibit operation of refueling stations, parking restrictions, application of LPG standards to LNG vehicles, and unintentionally unsafe vehicle or refueling station requirements; (3) need for clarification of EPA's tampering enforcement policy; (4) the U.S. hydrocarbon standard; (5) uncertainty concerning state utility commission jurisdiction; (6) sale for resale prohibitions imposed by natural gas utility companies or state utility commissions; (7) uncertainty of the effects of conversions to natural gas on vehicle manufactures warranties; and (8) need for a natural gas to gasoline equivalent units conversion factor for use in calculation of state road use taxes.

Jablonski, J.↗
NASA NTRS1994

Differential GPS and system integration of the Low Visibility Landing and Surface Operations (LVLASO) demonstration

The LVLASO Flight Demonstration of ASTA concepts (FDAC) integrates NASA-Langley's electronic moving map display and Transport Systems Research Vehicle (TSRV) (a modified Boeing 737 aircraft); ARINC's VHF data link, GPS ground station, and automated controller workstation; and Norden's surface radar/airport movement safety system. Aircraft location is shown on the electronic map display in the cockpit. An approved taxi route as well as other aircraft and surface traffic are also displayed. An Ashtech Z12 Global Positioning System (GPS) receiver on the TSRV estimates the aircraft's position. In Differential mode (DSPS), the Ashtech receiver accepts differential C/A code pseudorange corrections from a GPS ground station. The GPS ground station provides corrections up to ten satellites. The corrections are transmitted on a VHF data link at a 1 Hz. rate using the RTCM-104 format. DGPS position estimates will be within 5 meters of actual aircraft position. DGPS position estimates are blended with position, velocity, acceleration, and heading data from the TSRV Air Data/Inertial Reference System (ADIRS). The ADIRS data is accurate in the short-term, but drifts over time. The DGPS data is used to keep the ADIRS position accurate. Ownship position, velocity, heading, and turn rate are sent at a 20 Hz. rate to the electronic map display. Airport traffic is detected by the airport surface radar system. Aircraft and vehicles such as fuel trucks and baggage carts are detected. The traffic's location, velocity, and heading are sent to the TSRV. To prevent traffic symbology from jumping each second when a location update arrives, velocity and heading are used to predict a new traffic location for each display update. Possible runway incursions and collisions can be shown on the electronic map. Integrating the different systems used in the FDAC requires attention to the underlying coordinate systems. The airport diagram displayed on the electronic map is obtained from published navigational charts. The charts reference the North American Datum of 1927 (NAD27) or a local state-plane coordinate system. GPS uses the World Geodetic Standard of 1984 (WGS84). Both NAD27 and WGS84 model the Earth as an ellipsoid, however, they use a different origin and different size ellipsoids. Latitudes and longitudes given in these systems can be converted to a Cartesian system with the origin at the Earth's center. The surface radar detects traffic in a locally-level, rho-theta coordiante system. The electronic airport diagram is stored using a flat XY coordinate system. The map origin is at the tower and is referenced as True North up. All ownship and other traffic positions must be converted to the electronic map's frame of reference for display.

Rankin, James M.↗
NASA NTRS2009

Land-Use and Land-Cover Change around Mobile Bay, Alabama from 1974-2008

This document summarizes the major findings of a Gulf of Mexico Application Pilot project led by NASA Stennis Space Center (SSC) in conjunction with a regional collaboration network of the Gulf of Mexico Alliance (GOMA). NASA researchers processed and analyzed multi-temporal Landsat data to assess land-use and land-cover (LULC) changes in the coastal counties of Mobile and Baldwin, AL between 1974 and 2008. Our goal was to create satellite-based LULC data products using methods that could be transferable to other coastal areas of concern within the Gulf of Mexico. The Mobile Bay National Estuary Program (MBNEP) is the primary end-user, however, several other state and local groups may benefit from the project s data products that will be available through NOAA-NCDDC s Regional Ecosystem Data Management program. Mobile Bay is a critical ecologic and economic region in the Gulf of Mexico and to the entire country. Mobile Bay was designated as an estuary of national significance in 1996. This estuary receives the fourth largest freshwater inflow in the United States. It provides vital nursery habitat for commercially and recreationally important fish species. It has exceptional aquatic and terrestrial bio-diversity, however, its estuary health is influenced by changing LULC patterns, such as urbanization. Mobile and Baldwin counties have experienced a population growth of 1.1% and 20.5% from 2000-2006. Urban expansion and population growth are likely to accelerate with the construction and operation of the ThyssenKrupp steel mill in the northeast portion of Mobile County. Land-use and land-cover change can negatively impact Gulf coast water quality and ecological resources. The conversion of forest to urban cover types impacts the carbon cycle and increases the freshwater and sediment in coastal waters. Increased freshwater runoff decreases salinity and increases the turbidity of coastal waters, thus impacting the growth potential of submerged aquatic vegetation (SAV), which is critical nursing ground for many Gulf fish species. A survey of Mobile Bay SAV showed widespread decreases since the 1940s. Prior to our project, coastal environmental managers in Baldwin and Mobile counties needed more understanding of the historical LULC for properly assessing the impacts of urbanization. In particular, more information on the location and extent of changing urbanization LULC patterns was needed to aid LULC planning and to assess predictions of future LULC patterns. Our products will assist the coastal environmental managers and land-use planners in making better community growth planning decisions. Our project also will help to establish a historical baseline of LULC distributions, which is a fundamental need in any stewardship plan. The primary research objective of our project was to produce historic and current geospatial LULC change products across a 34-year time frame. A multi-decadal coastal LULC change product was the major project deliverable. The geographic extent and nature of change was quantified and assessed for the upland herbaceous, barren, open water, urban, upland forest, woody wetland, and non-woody wetlanddominated land cover types. We focused on regional analyses of decadal-scale urban expansion and watershed-scaled analyses of LULC change for multiple areas of concern to the Mobile Bay NEP (Figure A). We used the following dates to derive LULC classification products from Landsat data: 1974, 1979, 1984, 1988, 1991, 1996, 2001, 2005, and 2008. We assessed the accuracy of our products using randomly sampled locations and digital geospatial reference data including field survey data, high resolution orthorectified aerial photography, high resolution multispectral and panchromatic satellite data displays (from QuickBird and Corona sensors), digital elevation model data, and National Wetlands Inventory wetland cover type data. NOAA s Coastal Change Assessment Program s (C-CAP) and National Land Cover Database (NLCD) procts were used for qualitative comparison in assessing map accuracy. We calculated an average overall classification accuracy of 87% with similar overall accuracies for the older (MSS) and newer (TM and ETM) Landsat LULC products.

Ellis, Jean↗
DOE OSTI2024

Subsurface Energy Systems Mapping Inquiry Tool (MapIT)

The Subsurface Energy Systems Mapping Inquiry Tool (MapIT) is an online web mapping tool designed to help users discover available public-sourced data to facilitate data exploration for subsurface energy exploration and characterization efforts for resource identification (e.g. critical minerals, hydrocarbons, geothermal) as well as injection of geologic sequestration of carbon dioxide (e.g. enhanced oil recovery, saline storage, etc.). Modules within the tool curate data related to geology, faults, fractures, injection and confining zones, hydrologic information, groundwater, groundwater wells, geomechanical and petrophysical data, and geochemical data. User documentation on how to use the tool is also provided. Data have been collected from authoritative national, state, and local sources and made available in this tool. The data is also available as a data catalog and Esri Geodatabase at: https://edx.netl.doe.gov/dataset/mapit-database Disclaimer: There is no guarantee of completeness or appropriateness for individual user’s requirements. Use of this tool is solely at the discretion of the user. See full Federal Disclaimer for further information (https://netl.doe.gov/home/disclaimer). This project was funded by the United States Department of Energy, National Energy Technology Laboratory, in part, through a site support contract. Neither the United States Government nor any agency thereof, nor any of their employees, nor the support contractor, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. https://www.netl.doe.gov/home/disclaimer

Carbon Sequestration↗
NASA NTRS2018

Local Versus Remote Contributions of Soil Moisture to Near-Surface Temperature Variability

Soil moisture variations have a straightforward impact on overlying air temperatures, wetter soils can induce higher evaporative cooling of the soil and thus, locally, cooler temperatures overall. Not known, however, is the degree to which soil moisture variations can affect remote air temperatures through their impact on the atmospheric circulation. In this talk we describe a two-pronged analysis that addresses this question. In the first segment, an extensive ensemble of NASA/GSFC GEOS-5 atmospheric model simulations is analyzed statistically to isolate and quantify the contributions of various soil moisture states, both local and remote, to the variability of air temperature at a given local site. In the second segment, the relevance of the derived statistical relationships is evaluated by applying them to observations-based data. Results from the second segment suggest that the GEOS-5-based relationships do, at least to first order, hold in nature and thus may provide some skill to forecasts of air temperature at subseasonal time scales, at least in certain regions.

Koster, R.↗
DOE OSTI2025

Bridge connectivity effects on photoinduced ground-state electron spin polarization

Transient electron paramagnetic resonance (TREPR) spectroscopy has been used to probe photoinduced electron spin polarization in the recovered ground states of four radical-elaborated (CAT)Pt(bpy) donor-acceptor complexes (CAT = catechol; bpy = 4,4'-di-tert-butyl-2,2'-bipyridine). These complexes are comprised of one or two S = 1/2 nitronyl nitroxide radicals attached through different phenylethynyl bridges to the 3- or 3,6 positions of the CAT donor. In this paper, we demonstrate the effects of substitution patterns on the magnitude of the TREPR signal, thereby guiding future design principles for generating and understanding the origin of photoinduced electron spin polarization in these and related chromophores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Hot-Carrier Injection and Millisecond Charge Separation from a Robust Heteroleptic Iron(II) Chromophore Immobilized on TiO 2

The synthesis, spectroscopic characterization, computational analysis, and photoelectrochemical behavior of a new iron-based chromophore, [(Cpy) 2 Fe- (deeb)](PF 6 ) 2 (Fe(Cpy) 2 (deeb)), where Cpy is 1-methyl-3-(2-pyridyl)imidazole and deeb is 4,4’-(CO 2 CH 2 CH 3 ) 2 -2,2’-bipyridine, is reported. Electrochemically reversible waves assigned to a metal-centered E o (Fe III/II ) = +0.48 and a ligand-centered E o (Fe 2+/+ ) = −1.47 V vs Fc +/0 reduction were evident in cyclic voltammetry measurements. The combination of a strong σ-donor and a π-acceptor lowered the energy of the metal-toligand charge-transfer (MLCT) excited state relative to the metal-centered state. Two MLCT transitions appear in the visible region at 424 and 580 nm. TDDFT calculations revealed that the lower-energy band was well formulated as Fe(II)→deeb, and the higher-energy transition was charge transfer to both the deeb and Cpy ligands. Resonance Raman spectroscopy supports these findings showing enhanced deeb vibrational modes with 532 nm excitation, both deeb and Cpy modes with 473 nm excitation, and exclusively Cpy with 405 nm excitation. Ultrafast spectroscopy reveals a short-lived (∼2 ps) MLCT excited state and a longer-lived (∼20 ps) metal-centered state. Efficient methods to deprotect the ester groups and anchor the complex to mesoporous TiO 2 (anatase) thin films in high surface coverages, Fe(Cpy) 2 (dcb)|TiO 2 σ = 3 × 10 −8 mol/cm 2 , were established. Pulsed light excitation of Fe(Cpy) 2 (dcb)|TiO 2 resulted in rapid excited state injection (k inj > 10 8 s −1 ) and formation of a charge-separated state, Fe III (Cpy) 2 (dcb)|TiO 2 (e), which persists on the millisecond time scale before returning cleanly to the ground state with secondorder kinetics. Injection yields measured 50 ns after light excitation were found to double from Φ = 0.15 with green (532 nm) light to 0.30 with blue (457 nm) light excitation. Incident photon-to-current efficiency (% IPCE) measurements as a function of excitation wavelength in a 0.5 M LiI/I 2 /CH 3 CN electrolyte provide clear evidence for band-selective “hot carrier” injection from the remote Cpy-localized excited state. Collectively, the spectroscopic and photoelectrochemical data indicate that a semiconductor can intercept hot electrons from iron chromophores even when the excited-state dipole is oriented away from the surface-anchoring ligand.

Charge transfer↗