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1. Effect of R-site element on crystalline phase and thermal stability of Fe substituted Mn mullite-type oxides: R 2 (Mn 1−x Fe x ) 4 O 10−δ (R = Y, Sm or Bi; x = 0, 0.5, 1)

   https://doi.org/10.1039/C7RA09699B  

   Thampy, Sampreetha ; Ashburn, Nickolas ; Martin, Thomas J. ; Li, Chenzhe ; Zheng, Yongping ; Chan, Julia Y. ; Cho, Kyeongjae ; Hsu, Julia W. ( January 2018 , RSC Advances)

   Combining experimental and theoretical studies, we investigate the role of R-site (R = Y, Sm, Bi) element on the phase formation and thermal stability of R 2 (Mn 1−x Fe x ) 4 O 10−δ ( x = 0, 0.5, 1) mullite-type oxides. Our results show a distinct R-site dependent phase behavior for mullite-type oxides as Fe is substituted for Mn: 100% mullite-type phase was formed in (Y, Sm, Bi) 2 Mn 4 O 10 ; 55% and 18% of (Y, Sm) 2 Mn 2 Fe 2 O 10−δ was found when R = Y and Sm, respectively, for equal Fe and Mn molar concentrations in the reactants, whereas Bi formed 54% O10- and 42% O9-mixed mullite-type phases. Furthermore, when the reactants contain 100% Fe, no mullite-type phase was formed for R = Y and Sm, but a sub-group transition to Bi 2 Fe 4 O 9 O9-phase was found for R = Bi. Thermogravimetric analysis and density functional theory (DFT) calculation results show a decreasing thermal stability in O10-type structure with increasing Fe incorporation; for example, the decomposition temperature is 1142 K for Bi 2 Mn 2 Fe 2 O 10−δ vs. 1217 K for Bi 2 Mn 4 O 10 . On the other hand, Bi 2 Fe 4 O 9 O9-type structure is found to be thermally stable up to 1227 K. These findings are explained by electronic structure calculations: (1) as Fe concentration increases, Jahn–Teller distortion results in mid band-gap empty states from unstable Fe 4+ occupied octahedra, which is responsible for the decrease in O10 structure stability; (2) the directional sp orbital hybridization unique to Bi effectively stabilizes the mullite-type structure as Fe replaces Mn. 

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2. The reaction of alkyl hydropersulfides (RSSH, R = CH 3 and t Bu) with H 2 S in the gas phase and in aqueous solution

   https://doi.org/10.1039/C8CP05503C  

   Zhang, Linxing ; Zhang, Xinhao ; Wu, Yun-Dong ; Xie, Yaoming ; Fukuto, Jon M. ; Schaefer, Henry F. ( January 2019 , Physical Chemistry Chemical Physics)

   The RSSH + H 2 S → RSH + HSSH reaction has been suggested by numerous labs to be important in H 2 S-mediated biological processes. Seven different mechanisms for this reaction (R = CH 3 , as a model) have been studied using the DFT methods (M06-2X and ωB97X-D) with the Dunning aug-cc-pV(T+d)Z basis sets. The reaction of CH 3 SSH with gas phase H 2 S has a very high energy barrier (>45 kcal mol −1 ), consistent with the available experimental observations. A series of substitution reactions R 1 –S–S–H + − S–R 2 (R 1 = Me, t Bu, Ad, R 2 = H, S–Me, S– t Bu, S–Ad) have been studied. The regioselectivity is largely affected by the steric bulkiness of R 1 , but is much less sensitive to R 2 . Thus, when R 1 is Me, all − S–R 2 favorably attack the internal S atom, leading to R 1 –S–S–R 2 . While for R 1 = t Bu, Ad, all − S–R 2 significantly prefer to attack the external S atom to form − S–S–R 2 . These results are in good agreement with the experimental observations. 

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3. The Solar Minimum Eclipse of 2019 July 2. II. The First Absolute Brightness Measurements and MHD Model Predictions of Fe x, xi, and xiv out to 3.4 R ⊙

   https://doi.org/10.3847/1538-4357/ac8101  

   Boe, Benjamin ; Habbal, Shadia ; Downs, Cooper ; Druckmüller, Miloslav ( August 2022 , The Astrophysical Journal)

   We present the spatially resolved absolute brightness of the Fex, Fexi, and Fexivvisible coronal emission lines from 1.08 to 3.4R_⊙, observed during the 2019 July 2 total solar eclipse (TSE). The morphology of the corona was typical of solar minimum, with a dipole field dominance showcased by large polar coronal holes and a broad equatorial streamer belt. The Fexiline is found to be the brightest, followed by Fexand Fexiv(in diskB_⊙units). All lines had brightness variations between streamers and coronal holes, where Fexivexhibited the largest variation. However, Fexremained surprisingly uniform with latitude. The Fe line brightnesses are used to infer the relative ionic abundances and line-of-sight-averaged electron temperature (T_e) throughout the corona, yielding values from 1.25 to 1.4 MK in coronal holes and up to 1.65 MK in the core of streamers. The line brightnesses and inferredT_evalues are then quantitatively compared to the Predictive Science Inc. magnetohydrodynamic model prediction for this TSE. The MHD model predicted the Fe lines rather well in general, while the forward-modeled line ratios slightly underestimated the observationally inferredT_ewithin 5%–10% averaged over the entire corona. Larger discrepancies in the polar coronal holes may point to insufficient heating and/or other limitations in the approach. These comparisons highlight the importance of TSE observations for constraining models of the corona and solar wind formation.

    

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4. The β‐Agostic Structure in (C 5 Me 5 ) 2 Sc(CH 2 CH 3 ): Solid‐State NMR Studies of (C 5 Me 5 ) 2 Sc−R (R=Me, Ph, Et)

   https://doi.org/10.1002/anie.201805738  

   Culver, Damien B. ; Huynh, Winn ; Tafazolian, Hosein ; Ong, Ta‐Chung ; Conley, Matthew P. ( July 2018 , Angewandte Chemie International Edition)

   Multinuclear solid‐state NMR studies of Cp*₂Sc−R (Cp*=pentamethylcyclopentadienyl; R=Me, Ph, Et) and DFT calculations show that the Sc−Et complex contains a β‐CH agostic interaction. The static central transition⁴⁵Sc NMR spectra show that the quadrupolar coupling constants (C_q) follow the trend of Ph≈Me>Et, indicating that the Sc−R bond is different in Cp*₂Sc−Et compared to the methyl and phenyl complexes. Analysis of the chemical shift tensor (CST) shows that the deshielding experienced by Cβ in Sc−CH₂CH₃is related to coupling between the filled σ_C‐Corbital and the vacantorbital.

    

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5. The β‐Agostic Structure in (C 5 Me 5 ) 2 Sc(CH 2 CH 3 ): Solid‐State NMR Studies of (C 5 Me 5 ) 2 Sc−R (R=Me, Ph, Et)

   https://doi.org/10.1002/ange.201805738  

   Culver, Damien B. ; Huynh, Winn ; Tafazolian, Hosein ; Ong, Ta‐Chung ; Conley, Matthew P. ( July 2018 , Angewandte Chemie)

   Multinuclear solid‐state NMR studies of Cp*₂Sc−R (Cp*=pentamethylcyclopentadienyl; R=Me, Ph, Et) and DFT calculations show that the Sc−Et complex contains a β‐CH agostic interaction. The static central transition⁴⁵Sc NMR spectra show that the quadrupolar coupling constants (C_q) follow the trend of Ph≈Me>Et, indicating that the Sc−R bond is different in Cp*₂Sc−Et compared to the methyl and phenyl complexes. Analysis of the chemical shift tensor (CST) shows that the deshielding experienced by Cβ in Sc−CH₂CH₃is related to coupling between the filled σ_C‐Corbital and the vacantorbital.

    

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