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Creators/Authors contains: "Kelly, S"

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  1. Over the past decade, the proliferation of pulsed laser sources with high repetition rates has facilitated a merger of ultrafast time-resolved spectroscopy with imaging microscopy. In transient absorption microscopy (TAM), the excited-state dynamics of a system are tracked by measuring changes in the transmission of a focused probe pulse following photoexcitation of a sample. Typically, these experiments are done using a photodiode detector and lock-in amplifier synchronized with the laser and images highlighting spatial heterogeneity in the TAM signal are constructed by scanning the probe across a sample. Performing TAM by instead imaging a spatially defocused widefield probe with a multipixel camera could dramatically accelerate the acquisition of spatially resolved dynamics, yet approaches for such widefield imaging generally suffer from reduced signal-to-noise due to an incompatibility of multipixel cameras with high-frequency lock-in detection. Herein, we describe implementation of a camera capable of high-frequency lock-in detection, thereby enabling widefield TAM imaging at rates matching those of high repetition rate lasers. Transient images using a widefield probe and two separate pump pulse configurations are highlighted. In the first, a widefield probe was used to image changes in the spatial distribution of photoexcited molecules prepared by a tightly focused pump pulse, while in the second, a widefield probe detected spatial variations in photoexcited dynamics within a heterogeneous organic crystal excited by a defocused pump pulse. These results highlight the ability of high-sensitivity lock-in detection to enable widefield TAM imaging, which can be leveraged to further our understanding of excited-state dynamics and excitation transport within spatially heterogeneous systems. 
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  2. Abstract The National Ecological Observatory Network (NEON) provides over 180 distinct data products from 81 sites (47 terrestrial and 34 freshwater aquatic sites) within the United States and Puerto Rico. These data products include both field and remote sensing data collected using standardized protocols and sampling schema, with centralized quality assurance and quality control (QA/QC) provided by NEON staff. Such breadth of data creates opportunities for the research community to extend basic and applied research while also extending the impact and reach of NEON data through the creation of derived data products—higher level data products derived by the user community from NEON data. Derived data products are curated, documented, reproducibly‐generated datasets created by applying various processing steps to one or more lower level data products—including interpolation, extrapolation, integration, statistical analysis, modeling, or transformations. Derived data products directly benefit the research community and increase the impact of NEON data by broadening the size and diversity of the user base, decreasing the time and effort needed for working with NEON data, providing primary research foci through the development via the derivation process, and helping users address multidisciplinary questions. Creating derived data products also promotes personal career advancement to those involved through publications, citations, and future grant proposals. However, the creation of derived data products is a nontrivial task. Here we provide an overview of the process of creating derived data products while outlining the advantages, challenges, and major considerations. 
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    Free, publicly-accessible full text available January 1, 2026
  3. Time-resolved spectroscopy of plasmonic nanoparticles is a vital technique for probing their ultrafast electron dynamics and subsequent acoustic and photothermal properties. Traditionally, these experiments are performed with spectrally broad probe beams on the ensemble level to achieve high signal amplitudes. However, the relaxation dynamics of plasmonic nanoparticles is highly dependent on their size, shape, and crystallinity. As such, the inherent heterogeneity of most nanoparticle samples can complicate efforts to build microscopic models for these dynamics solely on the basis of ensemble measurements. Although approaches for collecting time-resolved microscopy signals from individual nanoparticles at selected probe wavelengths have been demonstrated, acquiring time-resolved spectra from single objects remains challenging. Here, we demonstrate an alternate method that efficiently yields the time-resolved spectra of a single gold nanodisk in one measurement. By modulating the frequency-doubled output of a 96 MHz Ti:sapphire oscillator at 8 kHz, we are able to use a lock-in pixel-array camera to detect photoinduced changes in the transmission of a white light continuum probe derived from a photonic crystal fiber to produce broadband femtosecond transmission spectra of a single gold nanodisk. We also compare the performance of the lock-in camera for the same single nanoparticle to measurements with a single-element photodiode and find comparable sensitivities. The lock-in camera thus provides a major advantage due to its ability to multiplex spectral detection, which we utilize here to capture both the electronic dynamics and acoustic vibrations of a single gold nanodisk following ultrafast laser excitation. 
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  4. The performance of a newKaband microwave spectrometer is demonstrated by investigating the rotational spectrum of methyltert-butyl ether, including isotopologues and a new torsionally excited state. 
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  5. This dataset contains estimates of gas exchange velocity, gas exchange rate, and hydraulic parameters for streams calculated from tracer-gas experiments and conservative tracer injections collected by the National Ecological Observatory Network (NEON). All input data were collected by NEON and is available on the NEON data portal at https://data.neonscience.org. Specifically, the NEON Reaeration field and lab collection data product (DP1.20190.001) was used to calculate these estimates. Gas exchange was estimated in two ways: first, following an unpooled frequentist approach and second, following a partially pooled Bayesian approach. In addition, a salt-correction was applied to gas exchange estimates for sites where it was possible and necessary. All estimates of gas exchange are included in the file gasExchange_ds.csv. A recommended selection of these estimates is included in the dataset (best_k600_mPerDay and best_K600_mPerDay). The stanfit objects used for the partially pooled Bayesian approach are also included as site-specific model objects for gas exchange velocities and rates. In addition, water velocity was calculated from conservative tracer injections, and mean water depth was calculated from these water velocity estimates and measurements of wetted width and water discharge. All hydraulic parameters are included in the file hydraulics_ds.csv. All processing code is available in the reaRates R package. NEON is sponsored by the National Science Foundation (NSF) and operated under cooperative agreement by Battelle. This material is based in part upon work supported by NSF through the NEON Program. 
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  6. Abstract. Air–water gas exchange is essential to understanding and quantifying many biogeochemical processes in streams and rivers, including greenhouse gas emissions and metabolism. Gas exchange depends on two factors, which are often quantified separately: (1) the air–water concentration gradient of the gas and (2) the gas exchange velocity.  There are fewer measurements of gas exchange velocity compared to concentrations in streams and rivers, which limits accurate characterization of air–water gas exchange (i.e., flux rates). The National Ecological Observatory Network (NEON) conducts SF6 gas-loss experiments in 22 of their 24 wadeable streams using standardized methods across all experiments and sites, and publishes raw concentration data from these experiments on the NEON data portal. NEON also conducts NaCl injections that can be used to characterize hydraulic geometry at all 24 wadeable streams. These NaCl injections are conducted both as part of the gas-loss experiments and separately. Here, we use these data to estimate gas exchange and water velocity using the reaRate R package. The dataset presented includes estimates of hydraulic parameters, cleaned raw concentration SF6 tracer-gas data (including removing outliers and failed experiments), estimated SF6 gas-loss rates, normalized gas exchange velocities (k600; m d−1) and normalized depth-dependent gas exchange rates (K600; d−1). This dataset provides one of the largest compilations of gas-loss experiments (n=339) in streams to date. This dataset is unique in that it contains gas exchange estimates from repeated experiments in geographically diverse streams across a range of discharges. In addition, this dataset contains information on the hydraulic geometry of all 24 NEON wadeable streams, which will support future research using NEON aquatic data. This dataset is a valuable resource that can be used to explore both within- and across-reach variability in the hydraulic geometry and gas exchange velocity in streams. The data are available at https://doi.org/10.6073/pasta/18dcc1871ee71cf0b69f2ee4082839d0 (Aho et al., 2024), and the reaRate R package code is available at https://doi.org/10.5281/zenodo.12786089 (Cawley et al., 2024). 
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  7. Nancy Grace Roman Space Telescope will revolutionize our understanding of the Galactic Bulge with its Galactic Bulge Time Domain survey. At the same time, Rubin Observatories's Legacy Survey of Space and Time (LSST) will monitor billions of stars in the Milky Way. The proposed Roman survey of the Galactic Plane, with its NIR passbands and exquisite spacial resolution, promises groundbreaking insights for a wide range of time-domain galactic astrophysics. In this white paper, we describe the scientific returns possible from the combination of the Roman Galactic Plane Survey with the data from LSST. 
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  8. Materials that undergo singlet fission are of interest for their use in light-harvesting, photocatalysis, and quantum information science, but their ability to undergo fission can be sensitive to local variations in molecular packing. Herein we employ transient absorption microscopy, molecular dynamics simulations, and electronic structure calculations to interrogate how structures found at the edges of orthorhombic rubrene crystals impact singlet fission. Within a micrometer-scale spatial region at the edges of rubrene crystals, we find that the rate of singlet fission increases nearly 4-fold. This observation is consistent with formation of a region at crystal edges with reduced order that accelerates singlet fission by disrupting the symmetry found in rubrene’s orthorhombic crystal structure. Our work demonstrates that structural distortions of singlet fission materials can be used to control fission in time and in space, potentially offering a means of controlling this process in light harvesting and quantum information applications. 
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