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1. Collision cross‐section analysis of self‐assembled metallomacrocycle isomers and isobars via ion mobility mass spectrometry

   https://doi.org/10.1002/rcm.8717  

   Endres, Kevin J. ; Barthelmes, Kevin ; Winter, Andreas ; Antolovich, Robert ; Schubert, Ulrich S. ; Wesdemiotis, Chrys ( February 2020 , Rapid Communications in Mass Spectrometry)

   Coordinatively driven self‐assembly of transition metal ions and bidentate ligands gives rise to organometallic complexes that usually contain superimposed isobars, isomers, and conformers. In this study, the double dispersion ability of ion mobility mass spectrometry (IM‐MS) was used to provide a comprehensive structural characterization of the self‐assembled supramolecular complexes by their mass and charge, revealed by the MS event, and their shape and collision cross‐section (Ω), revealed by the IM event.

   Self‐assembled complexes were synthesized by reacting a bis(terpyridine) ligand exhibiting a 60^odihedral angle between the two ligating terpyridine sites (T) with divalent Zn, Ni, Cd, or Fe. The products were isolated as (Metal²⁺[T])_n(PF₆)_2nsalts and analyzed using IM‐MS after electrospray ionization (ESI) which produced several charge states from eachn‐mer, depending on the number of PF₆ˉ anions lost upon ESI. Experimental Ω data, derived using IM‐MS, and computational Ω predictions were used to elucidate the size and architecture of the complexes.

   Only macrocyclic dimers, trimers, and tetramers were observed with Cd²⁺, whereas Zn²⁺formed the same plus hexameric complexes. These two metals led to the simplest product distributions and no linear isomers. In sharp contrast, Ni²⁺and Fe²⁺formed all possible ring sizes from dimer to hexamer as well as various linear isomers. The experimental and theoretical Ω data indicated rather planar macrocyclic geometries for the dimers and trimers, twisted 3D architectures for the larger rings, and substantially larger sizes with spiral conformation for the linear congeners. Adding PF₆ˉ to the same complex was found to mainly cause size contraction due to new stabilizing anion–cation interactions.

   Complete structural identification could be accomplished using ESI‐IM‐MS. Our results affirm that self‐assembly with Cd²⁺and Zn²⁺proceeds through reversible equilibria that generate the thermodynamically most stable structures, encompassing exclusively macrocyclic architectures that readily accommodate the 60^oligand used. In contrast, complexation with Ni²⁺and Fe²⁺, which form stronger coordinative bonds, proceeds through kinetic control, leading to more complex mixtures and kinetically trapped less stable architectures, such as macrocyclic pentamers and linear isomers.

    

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2. Laboratory Study of the Cameron Bands and UV Doublet in the Middle Ultraviolet 180–300 nm by Electron Impact upon CO 2 with Application to Mars

   https://doi.org/10.3847/1538-4357/ac88c8  

   Lee, Rena A. ; Ajello, Joseph M. ; Malone, Charles P. ; Evans, J. Scott ; Veibell, Victoir ; Holsclaw, Gregory M. ; McClintock, William E. ; Hoskins, Alan C. ; Jain, Sonal K. ; Gérard, Jean-Claude ; et al ( October 2022 , The Astrophysical Journal)

   We have observed electron impact fluorescence from CO₂to excite the Cameron bands (CBs), CO (a³Π →X¹Σ⁺; 180–280 nm), the first-negative group (1NG) bands, CO⁺(B²Σ⁺→X²Σ⁺; 180–320 nm), the fourth-positive group (4PG) bands, CO (A¹Π →X¹Σ⁺; 111–280 nm), and the UV doublet, CO₂⁺($\tilde{B}{}^2{\mathrm{\Sigma }}_u^{+}\to \tilde{X}{}^2{\mathrm{\Pi }}_g;$288.3 and 289.6 nm) in the ultraviolet (UV). This wavelength range matches the spectral region of past and present spacecraft equipped to observe UV dayglow and aurora emissions from the thermospheres (100–300 km) of Mars and Venus. Our large vacuum system apparatus is able to measure the emission cross sections of the strongest optically forbidden UV transitions found in planetary spectra. Based on our cross-sectional measurements, previous CB emission cross-sectional errors exceed a factor of 3. The UV doublet lifetime is perturbed through$\tilde{B}{}^2{\mathrm{\Sigma }}_u^{+}-\tilde{A}{}^2{\mathrm{\Pi }}_u$spin–orbit coupling. Forward modeling codes of the Mars dayglow have not been accurate in the mid-UV due to systematic errors in these two emission cross sections. We furnish absolute emission cross sections for several band systems over electron energies 20–100 eV for CO₂. We present a CB lifetime, which together with emission cross sections, furnish a set of fundamental physical constants for electron transport codes such as AURIC (Atmospheric Ultraviolet Radiance Integrated Code). AURIC and Trans-Mars are used in the analysis of UV spectra from the Martian dayglow and aurora.

    

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3. Pump Power Effects on Second Harmonic Stimulated Electromagnetic Emissions During Ionosphere Heating

   https://doi.org/10.1029/2019JA027282  

   Yellu, A. D. ; Scales, W. A. ; Mahmoudian, A. ; Bernhardt, P. A. ; Siefring, C. L. ; Briczinski, S. ; Nossa, E. ; McCarrick, M. J. ( November 2019 , Journal of Geophysical Research: Space Physics)

   Due to the potential for new diagnostic capabilities, there has been renewed interest in the generation of ionospheric stimulated electromagnetic emissions (SEEs) near the second harmonic of the pump frequency (ω₀), a process known as second harmonic generation (SHG). Observations of SHG during experiments at the High Frequency Active Auroral Research Program facility in whichω₀was stepped near the third harmonic of the electron gyrofrequency, 3ω_ce, and the transmit power linearly increased over the heating cycle at eachω₀, were reported recently. A key observation was the linkage between SEEs within ±30 Hz ofω₀, due to stimulated Brillouin scatter, and within ±30 Hz of 2ω₀. This current work reports further High Frequency Active Auroral Research Program observations that compare the time evolution of SEEs including SHG under the following two transmit power conditions (I) linear power ramp (II) maximum available power (2.8 MW). During these experiments,ω₀was stepped near 3ω_ceand also 2ω_ce. The results show that SEEs within ±100 Hz ofω₀and 2ω₀are both suppressed within a few seconds when the ionosphere is irradiated with the maximum available power. These SEEs appear to be suppressed before the onset of field‐aligned irregularities at the upper hybrid layer which is not in line with previous reports. Thus, other mechanisms, which are discussed, could possibly be responsible for the observed suppression of stimulated Brillouin scatter and SHG. Some preliminary diagnostics are derived from the SHG spectra temporal evolution by leveraging concepts from the field of laser plasma interactions.

    

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4. The Origin of Power-law Spectra in Relativistic Magnetic Reconnection

   https://doi.org/10.3847/2041-8213/acfe7c  

   Zhang, Hao ; Sironi, Lorenzo ; Giannios, Dimitrios ; Petropoulou, Maria ( October 2023 , The Astrophysical Journal Letters)

   Magnetic reconnection is often invoked as a source of high-energy particles, and in relativistic astrophysical systems it is regarded as a prime candidate for powering fast and bright flares. We present a novel analytical model—supported and benchmarked with large-scale three-dimensional kinetic particle-in-cell simulations in electron–positron plasmas—that elucidates the physics governing the generation of power-law energy spectra in relativistic reconnection. Particles with Lorentz factorγ≳ 3σ(here,σis the magnetization) gain most of their energy in the inflow region, while meandering between the two sides of the reconnection layer. Their acceleration time is$t_{\mathrm{acc}}\sim \gamma {\eta }_{\mathrm{rec}}^{-1}{\omega }_{\mathrm{c}}^{-1}\simeq 20\gamma {\omega }_{\mathrm{c}}^{-1}$, whereη_rec≃ 0.06 is the inflow speed in units of the speed of light andω_c=eB₀/mcis the gyrofrequency in the upstream magnetic field. They leave the region of active energization aftert_esc, when they get captured by one of the outflowing flux ropes of reconnected plasma. We directly measuret_escin our simulations and find thatt_esc∼t_accforσ≳ few. This leads to a universal (i.e.,σ-independent) power-law spectrum${\mathit{dN}}_{\mathrm{free}}/d\gamma \propto {\gamma }^{-1}$for the particles undergoing active acceleration, and$\mathit{dN}/d\gamma \propto {\gamma }^{-2}$for the overall particle population. Our results help to shed light on the ubiquitous presence of power-law particle and photon spectra in astrophysical nonthermal sources.

    

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5. Experimental and Theoretical Evidence of a Pb⋅⋅⋅Pb Ditetrel Bond Without a σ‐Hole

   https://doi.org/10.1002/cphc.202200306  

   Zierkiewicz, Wiktor ; Michalczyk, Mariusz ; Mahmoudi, Ghodrat ; García‐Santos, Isabel ; Castiñeiras, Alfonso ; Zangrando, Ennio ; Scheiner, Steve ( May 2022 , ChemPhysChem)

   The crystal structure of a newly synthesized compound, [PbL(Ac)]₂, (where L=2 (amino(pyrazin‐2‐yl) methylene) hydrazinecarbothioamide, Ac=acetate anion) exhibits a close contact between pairs of Pb atoms, suggesting a ditetrel bond, in addition to two Pb⋅⋅⋅O tetrel bonds, and two C−H⋅⋅⋅O H‐bonds. The presence of this ditetrel bond as an attractive component is confirmed by various quantum chemical methods. This novelty of this particular bond is its existence even in the absence of a σ‐hole on the Pb atom, which is typically considered a prerequisite for a bond of this type. From a wider perspective, a survey of the Cambridge Structural Database suggests this bond may be more common than was hitherto thought, with 44 examples of Pb⋅⋅⋅Pb contacts amongst a total number of 219 examples of T⋅⋅⋅T interactions in general (T=Si, Ge, Sn, Pb).

    

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