Correlation between 19F environment and isotropic chemical shift in barium and calcium fluoroaluminates

High-speed MAS (19)F NMR spectra are recorded and reconstructed for 10 compounds from BaF(2)-AlF(3) and CaF(2)-AlF(3) binary systems which leads to the determination of 77 isotropic (19)F chemical shifts in various environments. A first attribution of NMR lines is performed for 8 compounds using a superposition model as initially proposed by B. Bureau et al. The phenomenological parameters of this model are then refined to improve the NMR line assignment. A satisfactory reliability is reached with a root-mean-square (RMS) deviation between calculated and measured values equal to 6 ppm. The refined parameters are then successfully tested on alpha-BaCaAlF(7) whose structure was recently determined. Finally, the isotropic chemical shift ranges are defined for shared, unshared, and "free" fluorine atoms encountered in the investigated binary systems. So, the fluorine surroundings can be deduced from the NMR line positions in compounds whose structure is unknown. Such an approach can also be applied to fluoride glasses.     

An approximate ab initio SCFMO method

An approximate SCFMO method of calculation is presented which includes several features which are new to this type of approach. A minimal basis set of Slater type orbitals is used, and all integrals are included, but are evaluated approximately, using a series of analytical formulae which have been chosen to reproduce the rigorous values of the integrals. Results are given for the ground states of the H₂O, CH₄, BH₃, NH₃ and BeH₂ molecules, and are compared with previously calculated results.

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Zusammenfassung Eine Näherungs-SCF-MO-Rechnung mit einigen neuen Abänderungen wird vorgeschlagen. Eine minimale Basis von Slater-Orbitalen wird benutzt; es werden alle Integrale berücksichtigt, jedoch nur näherungsweise berechnet, wobei eine Reihe von analytischen Formeln benutzt wird, welche die exakten Werte der Integrale möglichst reproduzieren sollen. Ergebnisse für den Grundzustand von H₂O, CH₄, BH₃, NH₃ und BeH₂ werden mit früher berechneten Ergebnissen verglichen.

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Résumé Présentation d'une méthode SCF MO approchée comportant certaines caractéristiques nouvelles pour une telle méthode. On emploie une base minimale d'orbitales de Slater en ne négligeant aucune intégrale, mais en évaluant chaque intégrale d'une manière approchée au moyen d'une série de formules analytiques calibrées de manière à reproduire les valeurs exactes des intégrales. Les résultats obtenus pour les états fondamentaux de H₂O, CH₄, BH₃, NH₃ et BeH₂ sont comparés à ceux obtenus auparavant.

     

Electrochemical and photochemical approaches for the synthesis of the C28–C38 fragment of okadaic acid

Okadaic acid, a potent and selective inhibitor of Protein Phosphatases 1 and 2A (PP1 and PP2A), is widely used as a probe for various biochemical processes. We describe herein two innovative methods for the synthesis of the terminal C28–C38 fragment of the natural polyether. Suárez photochemical oxidative cyclization and electrochemical oxidation of malonates to their ketals equivalents have been successfully applied for the assembly of the key spiroketal core.     

19F high magnetic field NMR study of beta-ZrF4 and CeF4: from spectra reconstruction to correlation between fluorine sites and 19F isotropic chemical shifts

High magnetic field and high spinning frequency one- and two-dimensional one-pulse MAS 19F NMR spectra of beta-ZrF4 and CeF4 were recorded and reconstructed allowing the accurate determination of the 19F chemical shift tensor parameters for the seven different crystallographic fluorine sites of each compound. The attributions of the NMR resonances are performed using the superposition model for 19F isotropic chemical shift calculation initially proposed by Bureau et al. (Bureau, B.; Silly, G.; Emery, J.; Buzaré, J.-Y. Chem. Phys. 1999, 249, 85-104). A satisfactory reliability is reached with a root-mean-square (rms) deviation between calculated and measured isotropic chemical shift values equal to 1.5 and 3.5 ppm for beta-ZrF4 and CeF4, respectively.     

Ca(2+)/vacancies and O2-/F- ordering in new oxyfluoride pyrochlores Li(2x)Ca1.5-x square 0.5-xM2O6F (M = Nb,Ta) for 0 < or = x < or = 0.5

New oxyfluorides Li(2x)Ca(1.5-x) square (0.5-x)M2O6F (M = Nb, Ta), belonging to the cubic pyrochlore structural type (Z = 8, a approximately 10.5 angstroms), were synthesized by solid state reaction for 0 < or = x < or = 0.5. XRD data allowed us to determine their structures from single crystals for the two alpha and beta-Ca(1.5) square (0.5)Nb2O6F forms and from powder samples for the others. This characterisation was completed by TEM and solid state 19F NMR experiments. For the Ca(1.5) square (0.5)M2O6F (x = 0) pyrochlore phases, the presence of a double ordering phenomenon is demonstrated, involving on one hand the Ca(2+) ions and the vacancies and on the other hand the oxide and the fluoride anions which are strictly located in the 8b sites of the Fd3m aristotype space group. The Ca(2+) ions/vacancies ordering leads to a reversible phase transition, a (P4(3)32) <--> beta (Fd3m). The 19F NMR study strongly suggests that, in the beta-phases, the fluoride ions are only on average at the centre of the Ca3 square tetrahedron. It shows that slightly different Ca-F distances occuring in alpha-Ca(1.5) square (0.5)Nb2O6F may be related to a more difficult thermal ionic and vacancies diffusion process than in the tantalate compound. This may explain the hysteresis phenomenon presented by the phase transition. A solid solution Li(2x)Ca(1.5-x) square (0.5-x) Ta2O6F (0 < or = x < or = 0.5) was prepared and the order-disorder phase transition observed for Ca(1.5) square (0.5)M2MO6F compounds disappears for all the other compositions where less or no more vacancies exist in the 16d sites. In the LiCaM2O6F compounds, the 19F NMR study allows us to determine the Ca(2+) and Li+ ions distributions around the fluoride ions and shows that the [FLi2Ca2] environment is clearly favoured.     

Atomic Insights into Aluminium-Ion Insertion in Defective Anatase for Batteries

Aluminium batteries constitute a safe and sustainable high-energy-density electrochemical energy-storage solution. Viable Al-ion batteries require suitable electrode materials that can readily intercalate high-charge Al³⁺ ions. Here, we investigate the Al³⁺ intercalation chemistry of anatase TiO₂ and how chemical modifications influence the accommodation of Al³⁺ ions. We use fluoride- and hydroxide-doping to generate high concentrations of titanium vacancies. The coexistence of these hetero-anions and titanium vacancies leads to a complex insertion mechanism, attributed to three distinct types of host sites: native interstitial sites, single vacancy sites, and paired vacancy sites. We demonstrate that Al³⁺ induces a strong local distortion within the modified TiO₂ structure, which affects the insertion properties of the neighbouring host sites. Overall, specific structural features induced by the intercalation of highly polarising Al³⁺ ions should be considered when designing new electrode materials for polyvalent batteries.     

Thermal dynamics in the flux-coordinate independent turbulence code GRILLIX

GRILLIX employs the flux-coordinate independent approach (FCI), which allows us to study boundary plasma turbulence in realistic diverted configurations. Recently, the physical model in GRILLIX has been extended to a global drift-reduced Braginskii model, without any separation between background and fluctuations. It includes electromagnetic and thermal dynamics with hot ions, relaxation of the Boussinesq approximation and non-linear parametric dependencies. This contribution presents solutions to associated issues, that is, the ion diamagnetic polarization and the stiff parallel heat conduction. Simulations based on parameters characteristic for the Alcator C-Mod tokamak were carried out. In circular geometry, the self-consistent electric field contains zonal flows and geodesic acoustic modes in the confined region. In the scrape-off layer, the electron parallel heat conduction and its boundary condition determine the temperature and electric field, leading to sheared flows at the last closed flux surface.