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Future Lightning Instruments for Weather and Climate Monitoring From LEO

Lightning is not only a natural hazard, but it also holds information about physical processes at work in deep convection and influences atmospheric oxidants that modulate ozone and methane. Hence, spaceborne lightning observations are essential for monitoring extreme events and feedbacks in Earth’s climate system. Low-Earth orbiting (LEO) lightning mapping instruments established a 25-year record of global lightning activity and resulted in a wealth of studies that motivated its designation as an Essential Climate Variable by the World Meteorological Organization. Although geostationary observations of lightning have become increasingly available since 2017, LEO lightning mappers continue to serve critical needs given their unique vantage point and acceptance as a unifying reference for geostationary lightning mapper and ground-based global lightning datasets. At the close of 2023, the Lightning Imaging Sensor (LIS) will cease operations on the International Space Station, which introduces a critical gap in LEO-based monitoring of global lightning activity. To address this need, NASA is developing new lightning mapping technology that enables future LEO-based satellite missions. Existing LEO-based lightning mappers rely on narrowband optical emissions centered on 777.4-nm and detectors that capture 500 images per second to detect lightning both day and night. Lightning can also produce optical emissions in a narrowband centered on 337-nm without any corresponding emissions at the traditionally used near-infrared (NIR) wavelength. These near-ultraviolet (UV) emissions are associated with earlier stage electrical breakdown (e.g., streamers), may frequent intense regions of deep convective storms, and may be a significant source of nitrogen oxide production in the upper atmosphere. A new lightning mapping instrument called the CubeSat Lightning Imaging and Detection Experiment (CLIDE) is being designed at NASA Marshall Space Flight Center to use high-speed, scientific CMOS image sensors capable of detecting lightning’s transient optical emissions in the near-UV and NIR during both daylit and nighttime scenes. This will extend the record of global lightning activity and help pave the way for future small satellite missions that combine radio and optical lightning detectors to obtain novel three-dimensional maps of lightning on a global scale, which can revolutionize the way lightning is used to monitor weather and understand changes in climate.

lightning↗
DOE OSTI2021

Constraints on the Electromagnetic Counterpart of the Neutron-star–Black-hole Merger GW200115

We report the results of our follow-up campaign for the neutron-star—black-hole (NSBH) merger GW200115 detected during the O3 run of the Advanced LIGO and Advanced Virgo detectors. We obtained wide-field observations with the Deca-Degree Optical Transient Imager covering ~20% of the total probability area down to a limiting magnitude of w = 20.5 AB at ~23 hr after the merger. Our search for counterparts returns a single candidate (AT2020aeo), likely not associated with the merger. In total, only 25 sources of interest were identified by the community and later discarded as unrelated to the GW event. We compare our upper limits with the emission predicted by state-of-the-art kilonova simulations and disfavor high-mass ejecta (>0.1 M⊙), indicating that the spin of the system is not particularly high. By combining our optical limits with gamma-ray constraints from Swift and Fermi, we disfavor the presence of a standard short-duration burst for viewing angles ≲15° from the jet axis. Our conclusions are, however, limited by the large localization region of this GW event, and accurate prompt positions remain crucial to improving the efficiency of follow-up efforts.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2008

GOES-R Geostationary Lightning Mapper Performance Specifications and Algorithms

The Geostationary Lightning Mapper (GLM) is a single channel, near-IR imager/optical transient event detector, used to detect, locate and measure total lightning activity over the full-disk. The next generation NOAA Geostationary Operational Environmental Satellite (GOES-R) series will carry a GLM that will provide continuous day and night observations of lightning. The mission objectives for the GLM are to: (1) Provide continuous, full-disk lightning measurements for storm warning and nowcasting, (2) Provide early warning of tornadic activity, and (2) Accumulate a long-term database to track decadal changes of lightning. The GLM owes its heritage to the NASA Lightning Imaging Sensor (1997- present) and the Optical Transient Detector (1995-2000), which were developed for the Earth Observing System and have produced a combined 13 year data record of global lightning activity. GOES-R Risk Reduction Team and Algorithm Working Group Lightning Applications Team have begun to develop the Level 2 algorithms and applications. The science data will consist of lightning "events", "groups", and "flashes". The algorithm is being designed to be an efficient user of the computational resources. This may include parallelization of the code and the concept of sub-dividing the GLM FOV into regions to be processed in parallel. Proxy total lightning data from the NASA Lightning Imaging Sensor on the Tropical Rainfall Measuring Mission (TRMM) satellite and regional test beds (e.g., Lightning Mapping Arrays in North Alabama, Oklahoma, Central Florida, and the Washington DC Metropolitan area) are being used to develop the prelaunch algorithms and applications, and also improve our knowledge of thunderstorm initiation and evolution.

Mach, Douglas M.↗
DOE OSTI2025

Illuminating the Role of Alcohol Substrate in Nickel Photoredox Catalysis via Ground State and Transient Absorption Spectroscopy

Direct excitation of nickel photocatalysts has gained popularity over the last several years following the successful activation of nickel by Ir and Ru photosensitizers. The ability to pair these photosensitizers with Ni catalysts facilitates the formation of crucial chemical bonds under relatively mild conditions. However, there are still gaps in our understanding of what influences the performance of these Ni photocatalysts. Previous work from our group identified a nickel photocatalyst supported by a tridentate pyridinophane ligand that undergoes wavelength-dependent cross-coupling reactivity. Herein, we report detailed studies of the wavelength dependence of the C–O cross-coupling reactivity, illustrating that the catalytic activity has an optimal wavelength, and excitation on both the blue and red sides of this optimal wavelength leads to a reduction in product yield. We also reveal a crucial catalyst-alcohol preirradiation interaction that drastically alters the catalyst’s optical properties. Furthermore, we investigate both wavelength dependency and alcohol dependency via optical transient absorption spectroscopy and reveal a substrate binding process responsible for the observed wavelength-dependent cross-coupling catalysis.

alcohol↗
DOE OSTI2025

Spatio-spectral optical fission in time-varying subwavelength layers

Transparent conducting oxides are highly doped semiconductors that exhibit favourable optical features compared with metals, including reduced material losses, tuneable electronic and optical properties, and enhanced damage thresholds. Recently, the photonic community has renewed its attention towards these materials, recognizing their remarkable nonlinear optical properties in the near-infrared spectrum. The exceptionally large and ultrafast change in the refractive index, which can be optically induced in these compounds, extends beyond the boundaries of conventional perturbative analysis and makes this class of materials the closest approximation to a time-varying system. Here we report the spatio-spectral fission of an ultrafast pulse trespassing a thin film of aluminium zinc oxide with a non-stationary refractive index. By applying phase conservation to this time-varying layer, our model can account for both space and time refraction and explain, in quantitative terms, the spatial separation of both spectrum and energy. Our findings represent an example of extreme nonlinear phenomena on subwavelength propagation distances, which provides new insights into transparent conducting oxides’ transient optical properties. This can be critical for the ongoing research on photonic time crystals, on-chip generation of non-classical states of light, integrated optical neural networks, ultrafast beam steering and frequency-division multiplexing.

integrated optics↗
DOE OSTI2022

The most probable host of CHIME FRB 190425A, associated with binary neutron star merger GW190425, and a late-time transient search

The identification and localization of fast radio bursts (FRBs) to their host galaxies have revealed important details about the progenitors of these mysterious, millisecond-long bursts of coherent radio emission. In this work, we study the most probable host galaxy of the apparently non-repeating CHIME/FRB event FRB 20190425A – a particularly high-luminosity, low-dispersion measure event that was demonstrated in a recent paper to be temporally and spatially coincident with the LIGO-Virgo-KAGRA binary neutron star merger GW190425, suggesting an astrophysical association ( p -value 0.0052). In this paper, we remain agnostic to this result, and we confirm UGC10667 as the most probable host galaxy of FRB 20190425A, demonstrating that the host galaxies of low-dispersion measure, one-off CHIME FRBs can be plausibly identified. We then perform multiwavelength observations to characterize the galaxy and search for any afterglow emission associated with the FRB and its putative GW counterpart. We find no radio or optical transient emission in our observations 2.5 yr post-burst. UGC10667 is a spiral galaxy at z ∼ 0.03, dominated by an old stellar population. We find no evidence of a large population of young stars, with nebular emission dominated by star formation at a rate of 1 -2 M $\odot$ yr -1 . While we cannot rule out a young magnetar as the origin of FRB 20190425A, our observations are consistent with an origin in a long delay-time neutron star binary merger.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

Dynamics and observational signatures of core-collapse supernovae with central engines: hydrodynamics simulations with Monte Carlo post-processing

A long-lived central engine embedded in expanding supernova ejecta can alter the dynamics and observational signatures of the event, producing an unusually luminous, energetic, and/or rapidly evolving transient. We use 2D hydrodynamics simulations to study the effect of a central energy source, varying the amount, rate, and isotropy of the energy deposition. We post-process the results with a time-dependent Monte Carlo radiation transport code to extract observational signatures. The engine excavates a bubble at the centre of the ejecta, which becomes Rayleigh–Taylor unstable. Sufficiently powerful engines are able to break through the edge of the bubble and accelerate, shred, and compositionally mix the entire ejecta. The breakout of the engine-driven wind occurs at distinct rupture points, and the outflowing high-velocity gas may eventually give rise to radio emission. The dynamical impact of the engine leads to faster rising optical light curves, with photon escape facilitated by the faster expansion of the ejecta and the opening of low-density channels. For models with strong engines, the spectra are initially hot and featureless, but later evolve to resemble those of broad-line Ic supernovae. Under certain conditions, line emission from ionized, low-velocity material near the centre of the ejecta may be able to escape and produce narrow emission similar to that seen in interacting supernovae. We discuss how variability in the engine energy reservoir and injection rate could give rise to a heterogeneous set of events spanning multiple observational classes, including the fast blue optical transients, broad-line Ic supernovae, and superluminous supernovae.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2008

Pre-Launch Algorithms and Risk Reduction in Support of the Geostationary Lightning Mapper for GOES-R and Beyond

The Geostationary Lightning Mapper (GLM) is a single channel, near-IR imager/optical transient event detector, used to detect, locate and measure total lightning activity over the full-disk as part of a 3-axis stabilized, geostationary weather satellite system. The next generation NOAA Geostationary Operational Environmental Satellite (GOES-R) series with a planned launch in 2014 will carry a GLM that will provide continuous day and night observations of lightning from the west coast of Africa (GOES-E) to New Zealand (GOES-W) when the constellation is fUlly operational. The mission objectives for the GLM are to 1) provide continuous, full-disk lightning measurements for storm warning and nowcasting, 2) provide early warning of tornadic activity, and 3) accumulate a long-term database to track decadal changes of lightning. The GLM owes its heritage to the NASA Lightning Imaging Sensor (1997-Present) and the Optical Transient Detector (1995-2000), which were developed for the Earth Observing System and have produced a combined 13 year data record of global lightning activity. Instrument formulation studies were completed in March 2007 and the implementation phase to develop a prototype model and up to four flight models is expected to be underway in the latter part of 2007. In parallel with the instrument development, a GOES-R Risk Reduction Team and Algorithm Working Group Lightning Applications Team have begun to develop the Level 2 ground processing algorithms and applications. Proxy total lightning data from the NASA Lightning Imaging Sensor on the Tropical Rainfall Measuring Mission (TRMM) satellite and regional test beds (e.g., Lightning Mapping Arrays in North Alabama and the Washington DC Metropolitan area)

Goodman, Steven J.↗
NASA NTRS2008

Geostationary Lightning Mapper for GOES-R and Beyond

The Geostationary Lightning Mapper (GLM) is a single channel, near-IR imager/optical transient event detector, used to detect, locate and measure total lightning activity over the full-disk as part of a 3-axis stabilized, geostationary weather satellite system. The next generation NOAA Geostationary Operational Environmental Satellite (GOES-R) series with a planned launch readiness in December 2014 will carry a GLM that will provide continuous day and night observations of lightning from the west coast of Africa (GOES-E) to New Zealand (GOES-W) when the constellation is fUlly operational. The mission objectives for the GLM are to 1) provide continuous, full-disk lightning measurements for storm warning and nowcasting, 2) provide early warning of tornadic activity, and 3) accumulate a long-term database to track decadal changes of lightning. The GLM owes its heritage to the NASA Lightning Imaging Sensor (1997-Present) and the Optical Transient Detector (1995-2000), which were developed for the Earth Observing System and have produced a combined 13 year data record of global lightning activity. Instrument formulation studies were completed in March 2007 and the implementation phase to develop a prototype model and up to four flight models will be underway in the latter part of 2007. In parallel with the instrument development, a GOES-R Risk Reduction Team and Algorithm Working Group Lightning Applications Team have begun to develop the Level 2 algorithms and applications. Proxy total lightning data from the NASA Lightning Imaging Sensor on the Tropical Rainfall Measuring Mission (TRMM) satellite and regional test beds (e.g., Lightning Mapping Arrays in North Alabama and the Washington DC Metropolitan area) are being used to develop the pre-launch algorithms and applications, and also improve our knowledge of thunderstorm initiation and evolution. Real time lightning mapping data are being provided in an experimental mode to selected National Weather Service (NWS) forecast offices in Southern and Eastern Region. This effort is designed to help improve our understanding of the application of these data in operational settings.

Goodman, Steven J.↗
DOE OSTI2025

The luminous, slow-rising orphan afterglow AT2019pim as a candidate moderately relativistic outflow

ABSTRACT Classical gamma-ray bursts (GRBs) have two distinct emission episodes: prompt emission from ultrarelativistic ejecta and afterglow from shocked circumstellar material. While both components are extremely luminous in known GRBs, a variety of scenarios predict the existence of luminous afterglow emission with little or no associated high-energy prompt emission. We present AT 2019pim, the first spectroscopically confirmed afterglow with no observed high-energy emission to be identified. Serendipitously discovered during follow-up observations of a gravitational-wave trigger and located in a contemporaneous TESS sector, it is hallmarked by a fast-rising ($t \approx 2$ h), luminous ($M_{\rm UV,peak} \approx -24.4$ mag) optical transient with accompanying luminous X-ray and radio emission. No gamma-ray emission consistent with the time and location of the transient was detected by Fermi-GBM or by Konus, placing constraining limits on an accompanying GRB. We investigate several independent observational aspects of the afterglow in the context of constraints on relativistic motion and find all of them are consistent with an initial Lorentz factor of $\Gamma _0 \approx$ 10–30 for the on-axis material, significantly lower than in any well-observed GRB and consistent with the theoretically predicted ‘dirty fireball’ scenario in which the high-energy prompt emission is stifled by pair production. However, we cannot rule out a structured jet model in which only the line-of-sight material was ejected at low-$\Gamma$, off-axis from a classical high-$\Gamma$ jet core, and an on-axis GRB with below-average gamma-ray efficiency also remains a possibility. This event represents a milestone in orphan afterglow searches, demonstrating that luminous optical afterglows lacking detected GRB counterparts can be identified and spectroscopically confirmed in real time.

Perley, Daniel A. (ORCID:0000000184721996)↗
DOE OSTI2025

Highly Conjugated Porphyrin Arrays Enable Optical Resolution of Ferromagnetic and Antiferromagnetic Aligned States of the Triplet Exciton and an Incorporated Stable Radical

Well-defined photogenerated molecular spin systems have potential utility in spintronics and quantum information science (QIS). Because molecular magnetic, optical, and electronic properties can be controlled by design, diverse spin systems can be prepared at modest temperatures. Photogenerated molecular spin systems often involve states prepared from the interaction of excitons and charges. Resolving the nature of electron spin alignment in photogenerated spin states described by the coupling of a triplet exciton and a stable radical commonly relies on EPR spectroscopy. Here, we describe ethyne-bridged (porphinato)metal ( PM n ) oligomers that incorporate a macrocycle-bound Cu(II) radical center. Upon photoexcitation of such PM n arrays, a singdoublet ( 2 S 1 ) state is formed; ultrafast internal conversion (IC) then produces a tripdoublet ( 2 T 1 ) state, which undergoes intersystem crossing (ISC) to produce a tripquartet ( 4 T 1 ) state, before relaxation to the ground state ( 2 S 0 ). These highly conjugated Cu(II) radical-containing PMn arrays enable direct observation of copper porphyrin 2 T 1 → 4 T 1 ISC dynamics from the biexponential decay of the near-infrared (NIR) 2,4 T 1 → 2,4 T n transient absorption manifold. Multireference n-electron valence perturbation theory (NEVPT2) computations illuminate how PM n electronic structure controls the relaxation dynamics of these long-lived (>10 ns) electronically excited multiplet states. These studies show that highly conjugated and polarizable porphyrin arrays incorporating stable spin centers provide rare π-delocalized systems where the ferromagnetic and antiferromagnetic alignment between a triplet exciton and a stable radical are both spectrally resolved and addressable using transient optical spectroscopy at wavelengths exceeding 1 μm, providing new opportunities to QIS.

14 SOLAR ENERGY↗
DOE OSTI2021

Singlet fission and triplet pair recombination in bipentacenes with a twist

We investigate triplet pair dynamics in pentacene dimers that have varying degrees of coplanarity (pentacene–pentacene twist angle). The fine-tuning of the twist angle was achieved by alternating connectivity at the 1-position or 2-positions of pentacene. This mix-and-match connectivity leads to tunable twist angles between the two covalently linked pentacenes. These twisted dimers allow us to investigate the subtle effects that the dihedral angle between the covalently linked pentacenes imparts on singlet fission and triplet pair recombination dynamics. We observe that as the dihedral angle between the two bonded pentacenes is increased, the rates of singlet fission decrease, while the accompanying decrease in triplet recombination rates is stark. Temperature-dependent transient optical studies combined with theoretical calculations show that the triplet pair recombination proceeds primarily through a direct multiexciton internal conversion process. Calculations further show that the significant decrease in recombination rates can be directly attributed to a corresponding decrease in the magnitude of the nonadiabatic coupling between the singlet multiexcitonic state and the ground state. Furthermore, these results highlight the importance of the twist angle in designing systems that exhibit rapid singlet fission, while maintaining long triplet pair lifetimes in pentacene dimers.

14 SOLAR ENERGY↗
NASA NTRS2010

Combined Aircraft and Satellite-Derived Storm Electric Current and Lightning Rates Measurements and Implications for the Global Electric Circuit

Using rotating vane electric field mills and Gerdien capacitors, we measured the electric field profile and conductivity during 850 overflights of electrified shower clouds and thunderstorms spanning regions including the Southeastern United States, the Western Atlantic Ocean, the Gulf of Mexico, Central America and adjacent oceans, Central Brazil, and the South Pacific. The overflights include storms over land and ocean, with and without lightning, and with positive and negative fields above the storms. The measurements were made with the NASA ER-2 and the Altus-II high altitude aircrafts. Peak electric fields, with lightning transients removed, ranged from -1.0 kV/m to 16 kV/m, with a mean value of 0.9 kV/m. The median peak field was 0.29 kV/m. Integrating our electric field and conductivity data, we determined total conduction currents and flash rates for each overpass. With knowledge of the storm location (land or ocean) and type (with or without lightning), we determine the mean currents by location and type. The mean current for ocean storms with lightning is 1.6 A while the mean current for land storms with lightning is 1.0 A. The mean current for oceanic storms without lightning (i.e., electrified shower clouds) is 0.39 A and the mean current for land storms without lightning is 0.13 A. Thus, on average, land storms with or without lightning have about half the mean current as their corresponding oceanic storm counterparts. Over three-quarters (78%) of the land storms had detectable lightning, while less than half (43%) of the oceanic storms had lightning. We did not find any significant regional or latitudinal based patterns in our total conduction currents. By combining the aircraft derived storm currents and flash rates with diurnal lightning statistics derived from the Lightning Imaging Sensor (LIS) and Optical Transient Detector (OTD) low Earth orbiting satellites, we reproduce the diurnal variation in the global electric circuit (i.e., the Carnegie curve) to within 4% for all but two short periods of time. This excellent agreement with the Carnegie curve was obtained without any tuning or adjustment of the satellite or aircraft data. Given our data and assumptions, mean contributions to the global electric circuit are 0.7 kA (ocean) and 1.1 kA (land) from lightning-producing storms, and 0.22 kA (ocean) and 0.04 (land) from electrified shower clouds, resulting in a mean total conduction current estimate for the global electric circuit of 2.0 kA. Breaking the results down into mean storm counts reveals 1100 for land storms with lightning, 530 for ocean storms without lightning, 390 for ocean storms with lightning, and 330 for land storms without lightning.

Mach, Douglas M.↗
NASA NTRS2008

Total Lightning Observations of Extreme Weather Events over the Contiguous United States

The overall objective is to investigate total lightning characteristics of extreme weather events over the contiguous United States (CONUS) using TRMM (Tropical Rainfall Measuring Mission) LIS (Lightning Image Sensor) and OTD (Optical Transient Detector) satellite observations. A large LIS (10+ years) and OTD (5 years) data base is available to study the instantaneous total or cloud-to-ground (CG) plus intracloud (IC) lightning characteristics of extreme weather events. More specifically, the LIS and OTD data are combined with National Lightning Detection Network (NLDN) observations to examine the total and CG lightning flash rate and density, the IC:CG ratio, and positive CG percentage. These instantaneous lightning characteristics can be used for basic science studies to better understand the physical and dynamical linkages between lightning and precipitation and their environmental controls. They can also provide a first-look of extreme weather events leading up to future satellite observations (e.g., NOAA GOES-R Geostationary Lightning Mapper [GLM]) for use in climate studies and the short-term prediction and warning process. Extreme weather events are defined by the NOAA Storm Data reports of tornadoes, large hail (at least 0.75 inch) and strong straight-line winds (at least 50 kts). Over CONUS, there are over 70,000 severe storm reports in the TRMM spatial domain (< 35 N) from 1998-2007 and over 100,000 storm reports in the OTD spatial domain (5/1995-4/2000). Temporal co-location is on the order of 1% (i.e., 1000 s of coincident overpasses), providing a statistically significant sample of instantaneous total lightning properties. This instantaneous behavior of lightning in extreme weather is then compared to that of typical thunderstorm events, or randomly sampled LIS/OTD events in which the extreme events have been eliminated from the population. Results describing the instantaneous behavior of total lightning within a large sample of extreme and typical thunderstorms over CONUS will be presented. When possible, coincident VHF lightning observations from the ground-based Northern Alabama Lightning Mapping Array (LMA) are compared to the LIS/OTD optical lightning signatures, providing a validation source for instantaneous space-based optical lightning properties and a means to extend lightning inferences over the life-cycle of extreme weather.

Carey, Lawrence D.↗
DOE OSTI2023

Revealing Excited‐State Trajectories on Potential Energy Surfaces with Atomic Resolution in Real Time

Abstract Photoexcited molecular trajectories on potential energy surfaces (PESs) prior to thermalization are intimately connected to the photochemical reaction outcome. The excited‐state trajectories of a diplatinum complex featuring photo‐activated metal–metal σ ‐bond formation and associated Pt−Pt stretching motions were detected in real time using femtosecond wide‐angle X‐ray solution scattering. The observed motions correspond well with coherent vibrational wavepacket motions detected by femtosecond optical transient absorption. Two key coordinates for intersystem crossing have been identified, the Pt−Pt bond length and the orientation of the ligands coordinated with the platinum centers, along which the excited‐state trajectories can be projected onto the calculated PESs of the excited states. This investigation has gleaned novel insight into electronic transitions occurring on the time scales of vibrational motions measured in real time, revealing ultrafast nonadiabatic or non‐equilibrium processes along excited‐state trajectories involving multiple excited‐state PESs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Dominant Role of Hole Transport Pathway in Achieving Record High Photoconductivity in Two‐Dimensional Metal–Organic Frameworks

Abstract Metal–organic frameworks (MOFs) with mobile charges have attracted significant attention due to their potential applications in photoelectric devices, chemical resistance sensors, and catalysis. However, fundamental understanding of the charge transport pathway within the framework and the key properties that determine the performance of conductive MOFs in photoelectric devices remain underexplored. Herein, we report the mechanisms of photoinduced charge transport and electron dynamics in the conductive 2D M−HHTP (M=Cu, Zn or Cu/Zn mixed; HHTP=2,3,6,7,10,11‐hexahydroxytriphenylene) MOFs and their correlation with photoconductivity using the combination of time‐resolved terahertz spectroscopy, optical transient absorption spectroscopy, X‐ray transient absorption spectroscopy, and density functional theory (DFT) calculations. We identify the through‐space hole transport mechanism through the interlayer sheet π–π interaction, where photoinduced hole state resides in HHTP ligand and electronic state is localized at the metal center. Moreover, the photoconductivity of the Cu−HHTP MOF is found to be 65.5 S m −1 , which represents the record high photoconductivity for porous MOF materials based on catecholate ligands.

Wang, Denan↗
DOE OSTI2023

Revealing Excited‐State Trajectories on Potential Energy Surfaces with Atomic Resolution in Real Time

Abstract Photoexcited molecular trajectories on potential energy surfaces (PESs) prior to thermalization are intimately connected to the photochemical reaction outcome. The excited‐state trajectories of a diplatinum complex featuring photo‐activated metal–metal σ ‐bond formation and associated Pt−Pt stretching motions were detected in real time using femtosecond wide‐angle X‐ray solution scattering. The observed motions correspond well with coherent vibrational wavepacket motions detected by femtosecond optical transient absorption. Two key coordinates for intersystem crossing have been identified, the Pt−Pt bond length and the orientation of the ligands coordinated with the platinum centers, along which the excited‐state trajectories can be projected onto the calculated PESs of the excited states. This investigation has gleaned novel insight into electronic transitions occurring on the time scales of vibrational motions measured in real time, revealing ultrafast nonadiabatic or non‐equilibrium processes along excited‐state trajectories involving multiple excited‐state PESs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Dominant Role of Hole Transport Pathway in Achieving Record High Photoconductivity in Two‐Dimensional Metal–Organic Frameworks

Abstract Metal–organic frameworks (MOFs) with mobile charges have attracted significant attention due to their potential applications in photoelectric devices, chemical resistance sensors, and catalysis. However, fundamental understanding of the charge transport pathway within the framework and the key properties that determine the performance of conductive MOFs in photoelectric devices remain underexplored. Herein, we report the mechanisms of photoinduced charge transport and electron dynamics in the conductive 2D M−HHTP (M=Cu, Zn or Cu/Zn mixed; HHTP=2,3,6,7,10,11‐hexahydroxytriphenylene) MOFs and their correlation with photoconductivity using the combination of time‐resolved terahertz spectroscopy, optical transient absorption spectroscopy, X‐ray transient absorption spectroscopy, and density functional theory (DFT) calculations. We identify the through‐space hole transport mechanism through the interlayer sheet π–π interaction, where photoinduced hole state resides in HHTP ligand and electronic state is localized at the metal center. Moreover, the photoconductivity of the Cu−HHTP MOF is found to be 65.5 S m −1 , which represents the record high photoconductivity for porous MOF materials based on catecholate ligands.

14 SOLAR ENERGY↗