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1. Panning for Gold: New Emission Lines from UV–VIS Spectroscopy of Au I and Au II

   https://doi.org/10.3847/1538-4365/abaa4d  

   Bromley, S. J. ; Johnson, C. A. ; Ennis, D. A. ; Hartwell, G. J. ; Maurer, D. A. ; Loch, S.D. ; Stancil, P.C. ; McLaughlin, B. M. ; Sosolik, C. E. ; Marler, J. P. ( October 2020 , The astrophysical journal)

   The recent detection of a neutron star merger by the LIGO collaboration has renewed interest in laboratory studies of r-process elements. Accurate modeling and interpretation of the electromagnetic transients following the mergers requires computationally expensive calculations of both the structure and opacity of all trans-iron elements. To date, the necessary atomic data to benchmark structure codes are incomplete or, in some cases, absent entirely. Within the available laboratory studies, the literature on Au I and Au II provides incomplete reports of the emission lines and level structures. We present a new study of Au I and Au II lines and levels by exposing a solid gold target to plasma in the Compact Toroidal Hybrid (CTH) experiment at Auburn University. A wavelength range from 187 to 800 nm was studied. In Au I, 86 lines are observed, 43 of which are unreported in the literature, and the energies of 18 5d9 6s 6p levels and 16 of the 18 known 5d9 6s 6d levels are corroborated by a least-squares level energy optimization. In Au II, 76 emission lines are observed, and 51 of the lines are unreported in the literature. For both Au I and Au II, the new lines predominantly originate from the most energetic of the known levels, and over half of the new Au II lines have wavelengths longer than 300 nm. For the estimated electron parameters of CTH plasmas at the gold target (ne~10^12 cm−3, Te~10 eV), two-electron transitions are similar in intensity to LS-allowed one-electron transitions. 

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2. Bright NIR‐II Photoluminescence in Rod‐Shaped Icosahedral Gold Nanoclusters

   https://doi.org/10.1002/smll.202007992  

   Li, Qi ; Zeman, IV, Charles J. ; Ma, Zhuoran ; Schatz, George C. ; Gu, X. Wendy ( February 2021 , Small)

   Fluorophores with high quantum yields, extended maximum emission wavelengths, and long photoluminescence (PL) lifetimes are still lacking for sensing and imaging applications in the second near‐infrared window (NIR‐II). In this work, a series of rod‐shaped icosahedral nanoclusters with bright NIR‐II PL, quantum yields up to≈8%, and a peak emission wavelength of 1520 nm are reported. It is found that the bright NIR‐II emission arises from a previously ignored state with near‐zero oscillator strength in the ground‐state geometry and the central Au atom in the nanoclusters suppresses the non‐radiative transitions and enhances the overall PL efficiency. In addition, a framework is developed to analyze and relate the underlying transitions for the absorptions and the NIR‐II emissions in the Au nanoclusters based on the experimentally defined absorption coefficient. Overall, this work not only shows good performance of the rod‐shaped icosahedral series of Au nanoclusters as NIR‐II fluorophores, but also unravels the fundamental electronic transitions and atomic‐level structure‐property relations for the enhancement of the NIR‐II PL in gold nanoclusters. The framework developed here also provides a simple method to analyze the underlying electronic transitions in metal nanoclusters.

    

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3. Atomic data calculations for Au i –Au iii and exploration in the application of collisional-radiative theory to laboratory and neutron star merger plasmas

   https://doi.org/10.1093/mnras/stab3285  

   McCann, Michael ; Bromley, S ; Loch, S D ; Ballance, C P ( December 2021 , Monthly Notices of the Royal Astronomical Society)

   ABSTRACT Neutron binary star mergers have long been proposed as sufficiently neutron rich environments that could support the synthesis of rapid neutron capture elements (r-process elements) such as gold. However, the literature reveals that beyond neutral and singly ionized systems, there is an incompleteness of atomic data for the remaining ion stages of importance for mergers. In this work, we report on relativistic atomic structure calculations for Au i–Au iii using the grasp0 codes. Comparisons to calculations using the Flexible Atomic Code suggest uncertainties on average of 9.2 per cent, 5.7 per cent, and 3.8 per cent for Au i–Au iii level energies. Agreement around ∼50 per cent is achieved between our computed A-values and those in the literature, where available. Using the grasp0 structure of Au i, we calculated electron-impact excitation rate coefficients and use a collisional-radiative model to explore the excitation dynamics and line ratio diagnostics possible in neutron star merger environments. We find that proper accounting of metastable populations is critical for extracting useful information from ultraviolet–visible line ratio diagnostics of Au i. As a test of our data, we applied our electron-impact data to study a gold hollow cathode spectrum in the literature and diagnosed the plasma conditions as Te = 3.1 ± 1.2 eV and $n_\textrm {e} = 2.7^{+1.3}_{-0.9}\times 10^{13}$ cm−3. 

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4. Ligand removal energetics control CO 2 electroreduction selectivity on atomically precise, ligated alloy nanoclusters

   https://doi.org/10.1039/d2en00157h  

   Rybacki, Malena ; Nagarajan, Anantha Venkataraman ; Mpourmpakis, Giannis ( June 2022 , Environmental Science: Nano)

   Atomically precise, thiolate-protected gold nanoclusters (TPNCs) exhibit remarkable catalytic performance for the electrochemical reduction of carbon dioxide (CO 2 R) to CO. The origin of their high CO 2 R activity and selectivity has been attributed to partial ligand removal from the thiolate-covered surfaces of TPNCs to expose catalytically active sulfur atoms. Recently, heterometal doped (alloy) TPNCs have been shown to exhibit enhanced CO 2 R activity and selectivity compared to their monometallic counterparts. However, systematic studies on the effect of doping (metal type and location on TPNC) on active site exposure and CO 2 R activity are missing in literature. Herein, we apply Density Functional Theory calculations to investigate the effect of heterometal (Pt, Pd, Hg and Cd) doping of Au 25 (SR) 18 TPNC on the active site exposure and CO 2 R activity and selectivity. We reveal that doping significantly modifies relevant TPNC electronic properties, such as electron affinity, while also altering partial ligand removal and carboxyl (*COOH) intermediate formation energies. Furthermore, we demonstrate that changing the dopant ( e.g. Hg) position can change the selectivity of the TPNC towards CO (g) or H 2(g) formation, highlighting the importance of dopant locations in TPNC-based CO 2 R. Most notably, we report a universal ( i.e. capturing different dopant types and positions) linear trend between the ligand removal energy and i) the *COOH formation energy, as well as, ii) the hydrogen (*H) formation energy on the different alloy TPNCs. Thus, utilizing the ligand removal energy as a descriptor for CO 2 RR activity and selectivity, our work opens new avenues for accelerated computational screening of different alloy TPNCs for electrocatalytic CO 2 R applications. 

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5. Extreme Ultraviolet Reflection-Absorption (XUV-RA) Spectroscopy: Probing Dynamics at Surfaces from a Molecular Perspective

   https://doi.org/https://doi.org/10.1021/acs.accounts.1c00765  

   Biswas, Somnath ; Baker, L. Robert ( March 2022 , Accounts of chemical research)

   Extreme ultraviolet (XUV) light sources based on high harmonic generation are enabling the development of novel spectroscopic methods to help advance the frontiers of ultrafast science and technology. In this account we discuss the development of XUV-RA spectroscopy at near grazing incident reflection geometry and highlight recent applications of this method to study ultrafast electron dynamics at surfaces. Measuring core-to-valence transitions with broadband, femtosecond pulses of XUV light extends the benefits of x-ray absorption spectroscopy to a laboratory tabletop by providing a chemical fingerprint of materials, including the ability to resolve individual elements with sensitivity to oxidation state, spin state, carrier polarity, and coordination geometry. Combining this chemical state sensitivity with femtosecond time resolution provides new insight into the material properties that govern charge carrier dynamics in complex materials. It is well known that surface dynamics differ significantly from equivalent processes in bulk materials, and that charge separation, trapping, transport, and recombination occurring uniquely at surfaces governs the efficiency of numerous technologically relevant processes spanning photocatalysis, photovoltaics, and information storage and processing. Importantly, XUV-RA spectroscopy at near grazing angle is also surface sensitive with a probe depth of 3 nm, providing a new window into electronic and structural dynamics at surfaces and interfaces. Here we highlight the unique capabilities and recent applications of XUVRA spectroscopy to study photo-induced surface dynamics in metal oxide semiconductors, including photocatalytic oxides (Fe2O3, Co3O4 NiO, and CuFeO2) as well as photoswitchable magnetic oxide (CoFe2O4). We first compare the ultrafast electron self-trapping rates via small polaron formation at the surface and bulk of Fe2O3 where we note that the energetics and kinetics of this process differ significantly at the surface. Additionally, we demonstrate the ability to systematically tune this kinetics by molecular functionalization, thereby, providing a route to control carrier transport at surfaces. We also measure the spectral signatures of charge transfer excitons with site specific localization of both electrons and holes in a series of transition metal oxide semiconductors (Fe2O3, NiO, Co3O4). The presence of valence band holes probed at the oxygen L1-edge confirms a direct relationship between the metal-oxygen bond covalency and water oxidation efficiency. For a mixed metal oxide CuFeO2 in the layered delafossite structure, XUV-RA reveals that the sub-picosecond hole thermalization from O 2p to Cu 3d states of CuFeO2 leads to the spatial separation of electrons and holes, resulting in exceptional photocatalytic performance for H2 evolution and CO2 reduction of this material. Finally, we provide an example to show the ability of XUV-RA to probe spin state specific dynamics in a the photo-switchable ferrimagnet, cobalt ferrite (CoFe2O4). This study provides a detailed understating of ultrafast spin switching in a complex magnetic material with site-specific resolution. In summary, the applications of XUV-RA spectroscopy demonstrated here illustrate the current abilities and future promise of this method to extend molecule-level understanding from well-defined photochemical complexes to complex materials so that charge and spin dynamics at surfaces can be tuned with the precision of molecular photochemistry. 

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