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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 predominantlymore »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.« less
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.
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.
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.more »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.« less
5. Excitation mechanisms in the intracluster filaments surrounding brightest cluster galaxies

   https://doi.org/10.1051/0004-6361/202039730  

   Polles, F. L. ; Salomé, P. ; Guillard, P. ; Godard, B. ; Pineau des Forêts, G. ; Olivares, V. ; Beckmann, R. S. ; Canning, R. E. ; Combes, F. ; Dubois, Y. ; et al ( July 2021 , Astronomy & Astrophysics)

   Context. The excitation of the filamentary gas structures surrounding giant elliptical galaxies at the center of cool-core clusters, also known as brightest cluster galaxies (BCGs), is key to our understanding of active galactic nucleus (AGN) feedback, and of the impact of environmental and local effects on star formation. Aims. We investigate the contribution of thermal radiation from the cooling flow surrounding BCGs to the excitation of the filaments. We explore the effects of small levels of extra heating (turbulence), and of metallicity, on the optical and infrared lines. Methods. Using the C LOUDY code, we modeled the photoionization and photodissociation of a slab of gas of optical depth A V  ≤ 30 mag at constant pressure in order to calculate self-consistently all of the gas phases, from ionized gas to molecular gas. The ionizing source is the extreme ultraviolet (EUV) and soft X-ray radiation emitted by the cooling gas. We tested these models comparing their predictions to the rich multi-wavelength observations from optical to submillimeter, now achieved in cool core clusters. Results. Such models of self-irradiated clouds, when reaching sufficiently large A V , lead to a cloud structure with ionized, atomic, and molecular gas phases. These models reproduce most ofmore »the multi-wavelength spectra observed in the nebulae surrounding the BCGs, not only the low-ionization nuclear emission region like optical diagnostics, [O  III ] λ 5007 Å/H β , [N  II ] λ 6583 Å/H α , and ([S  II ] λ 6716 Å+[S  II ] λ 6731 Å)/H α , but also the infrared emission lines from the atomic gas. [O  I ] λ 6300 Å/H α , instead, is overestimated across the full parameter space, except for very low A V . The modeled ro-vibrational H 2 lines also match observations, which indicates that near- and mid-infrared H 2 lines are mostly excited by collisions between H 2 molecules and secondary electrons produced naturally inside the cloud by the interaction between the X-rays and the cold gas in the filament. However, there is still some tension between ionized and molecular line tracers (i.e., CO), which requires optimization of the cloud structure and the density of the molecular zone. The limited range of parameters over which predictions match observations allows us to constrain, in spite of degeneracies in the parameter space, the intensity of X-ray radiation bathing filaments, as well as some of their physical properties like A V or the level of turbulent heating rate. Conclusions. The reprocessing of the EUV and X-ray radiation from the plasma cooling is an important powering source of line emission from filaments surrounding BCGs. C LOUDY self-irradiated X-ray excitation models coupled with a small level of turbulent heating manage to simultaneously reproduce a large number of optical-to-infrared line ratios when all the gas phases (from ionized to molecular) are modeled self-consistently. Releasing some of the simplifications of our model, like the constant pressure, or adding the radiation fields from the AGN and stars, as well as a combination of matter- and radiation-bounded cloud distribution, should improve the predictions of line emission from the different gas phases.« less