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1. Branching Ratio for O + H ₃ ⁺ Forming OH ⁺ + H ₂ and H ₂ O ⁺ + H

   https://doi.org/10.3847/1538-4357/ac41ce  

   Hillenbrand, Pierre-Michel; Ruette, Nathalie de; Urbain, Xavier; Savin, Daniel W. (March 2022, The Astrophysical Journal)

   Abstract The gas-phase reaction of O + H 3 + has two exothermic product channels: OH + + H 2 and H 2 O + + H. In the present study, we analyze experimental data from a merged-beams measurement to derive thermal rate coefficients resolved by product channel for the temperature range from 10 to 1000 K. Published astrochemical models either ignore the second product channel or apply a temperature-independent branching ratio of 70% versus 30% for the formation of OH + + H 2 versus H 2 O + + H, respectively, which originates from a single experimental data point measured at 295 K. Our results are consistent with this data point, but show a branching ratio that varies with temperature reaching 58% versus 42% at 10 K. We provide recommended rate coefficients for the two product channels for two cases, one where the initial fine-structure population of the O( 3 P J ) reactant is in its J = 2 ground state and the other one where it is in thermal equilibrium. 

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2. Observation of Transition‐Metal–Boron Triple Bonds in IrB ₂ O ⁻ and ReB ₂ O ⁻

   https://doi.org/10.1002/anie.202006652  

   Chen, Teng‐Teng; Cheung, Ling Fung; Chen, Wei‐Jia; Cavanagh, Joseph; Wang, Lai‐Sheng (June 2020, Angewandte Chemie International Edition)

   Abstract Multiple bonds between boron and transition metals are known in many borylene (:BR) complexes via metal d_π→BR back‐donation, despite the electron deficiency of boron. An electron‐precise metal–boron triple bond was first observed in BiB₂O⁻[Bi≡B−B≡O]⁻in which both boron atoms can be viewed as sp‐hybridized and the [B−BO]⁻fragment is isoelectronic to a carbyne (CR). To search for the first electron‐precise transition‐metal‐boron triple‐bond species, we have produced IrB₂O⁻and ReB₂O⁻and investigated them by photoelectron spectroscopy and quantum‐chemical calculations. The results allow to elucidate the structures and bonding in the two clusters. We find IrB₂O⁻has a closed‐shell bent structure (C_s,¹A′) with BO⁻coordinated to an Ir≡B unit, (⁻OB)Ir≡B, whereas ReB₂O⁻is linear (C_∞v,³Σ⁻) with an electron‐precise Re≡B triple bond, [Re≡B−B≡O]⁻. The results suggest the intriguing possibility of synthesizing compounds with electron‐precise M≡B triple bonds analogous to classical carbyne systems. 

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3. Hydrated Sulfate Clusters SO ₄ ^2– (H ₂ O) _n ( n = 1–40): Charge Distribution Through Solvation Shells and Stabilization

   https://doi.org/10.1021/acs.jpcb.9b01744  

   Kulichenko, Maksim; Fedik, Nikita; Bozhenko, Konstantin V.; Boldyrev, Alexander I. (April 2019, The Journal of Physical Chemistry B)
4. Electrical properties of α-Ga ₂ O ₃ films grown by halide vapor phase epitaxy on sapphire with α-Cr ₂ O ₃ buffers

   https://doi.org/10.1063/5.0090832  

   Polyakov, Alexander; Nikolaev, Vladimir; Stepanov, Sergey; Almaev, Alexei; Pechnikov, Alexei; Yakimov, Eugene; Kushnarev, Bogdan O.; Shchemerov, Ivan; Scheglov, Mikhail; Chernykh, Alexey; et al (June 2022, Journal of Applied Physics)

   We report on growth and electrical properties of α-Ga₂O₃films prepared by halide vapor phase epitaxy (HVPE) at 500 °C on α-Cr₂O₃buffers predeposited on sapphire by magnetron sputtering. The α-Cr₂O₃buffers showed a wide microcathodoluminescence (MCL) peak near 350 nm corresponding to the α-Cr₂O₃bandgap and a sharp MCL line near 700 nm due to the Cr⁺intracenter transition. Ohmic contacts to Cr₂O₃were made with both Ti/Au or Ni, producing linear current–voltage ( I– V) characteristics over a wide temperature range with an activation energy of conductivity of ∼75 meV. The sign of thermoelectric power indicated p-type conductivity of the buffers. Sn-doped, 2- μm-thick α-Ga₂O₃films prepared on this buffer by HVPE showed donor ionization energies of 0.2–0.25 eV, while undoped films were resistive with the Fermi level pinned at E_Cof 0.3 eV. The I– V and capacitance–voltage ( C– V) characteristics of Ni Schottky diodes on Sn-doped samples using a Cr₂O₃buffer indicated the presence of two face-to-face junctions, one between n-Ga₂O₃and p-Cr₂O₃, the other due to the Ni Schottky diode with n-Ga₂O₃. The spectral dependence of the photocurrent measured on the structure showed the presence of three major deep traps with optical ionization thresholds near 1.3, 2, and 2.8 eV. Photoinduced current transient spectroscopy spectra of the structures were dominated by deep traps with an ionization energy of 0.95 eV. These experiments suggest another pathway to obtain p–n heterojunctions in the α-Ga₂O₃system. 

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5. Ab initio determination of a simultaneous dual-ion charging mechanism for Ni _0.25 Mn _0.75 O ₂ through redox reactions of Ni ²⁺ /Ni ⁴⁺ and O ^2- /O ^-

   https://doi.org/10.1039/D2TA03938A  

   Shepard, Robert; Brennan, Scott; Juran, Taylor R; Young, Joshua; Smeu, Manuel (July 2022, Journal of Materials Chemistry A)

   Over recent years, great efforts have been made to push the limits of layered transition metal oxides for secondary battery cathodes. This is particularly true for overall capacity, which has reached a terminal theoretical value for many materials. One avenue for increasing this capacity during charging is the intercalation of anions post cation deintercalation. This work investigates the charging mechanism of the P3-Na0.5Ni0.25 Mn0.75O2 cathode material through cation (Na) deintercalation and anion (ClO4) intercalation by means of density functional theory. The calculations corroborate experimental findings of increased capacity (135 mAh g-1 to 180 mAh g-1) through the intercalation of anions. However, this work demonstrates that a process of simultaneous cation deintercalation/anion intercalation is the primary charging mechanism, with charge compensation reactions of Ni2+/Ni4+ and O2-/O- occurring within the cathode material. To elucidate this simultaneous process, a novel method for computationally determining anion voltage in which one must consider full electrolyte interactions is proposed. Based on the results, it is believed that a simultaneous cation deintercalation/anion intercalation mechanism provides one potential avenue for the discovery of the next generation of secondary batteries. 

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