title: NMR parameters in column 13 metal fluoride compounds (AlF₃, GaF₃, InF₃ and TlF) from first principle calculations.
abstract: The relationship between the experimental (19)F isotropic chemical shift and the (19)F isotropic shielding calculated using the gauge including projector augmented-wave (GIPAW) method with PBE functional is investigated in the case of GaF3, InF3, TlF and several AlF3 polymorphs. It is shown that the linear correlation between experimental and DFT-PBE calculated values previously established on alkali, alkaline earth and rare earth of column 3 basic fluorides (Sadoc et al., Phys. Chem. Chem. Phys. 13 (2011) 18539-18550) remains valid in the case of column 13 metal fluorides, indicating that it allows predicting (19)F solid state NMR spectra of a broad range of crystalline fluorides with a relatively good accuracy. For the isostructural α-AlF3, GaF3 and InF3 phases, PBE-DFT geometry optimization leads to noticeably overbended M-F-M bond angles and underestimated (27)Al, (71)Ga and (115)In calculated quadrupolar coupling constants. For the studied compounds, whose structures are built of corner shared MF6 octahedra, it is shown that the electric field gradient (EFG) tensor at the cationic sites is not related to distortions of the octahedral units, in contrast to what previously observed for isolated AlF6 octahedra in fluoroaluminates.
authors: Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3, France.
authors: Aymeric
authors: A
authors: Sadoc
authors: LUNAM Université, Université du Maine, CNRS UMR 6283, Institut des Molécules et des Matériaux du Mans, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France.
authors: Mamata
authors: M
authors: Biswal
authors: LUNAM Université, Université du Maine, CNRS UMR 6283, Institut des Molécules et des Matériaux du Mans, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France.
authors: Monique
authors: M
authors: Body
authors: LUNAM Université, Université du Maine, CNRS UMR 6283, Institut des Molécules et des Matériaux du Mans, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France. Electronic address: christophe.legein@univ-lemans.fr.
authors: Christophe
authors: C
authors: Legein
authors: Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3, France.
authors: Florent
authors: F
authors: Boucher
authors: Conditions Extrêmes et Matériaux: Haute Température et Irradiation, CNRS UPR 3079, 1D Avenue de la Recherche Scientifique, 45071 Orléans Cedex 2, France; Université d'Orléans, Faculté des Sciences, Avenue du Parc Floral, 45067 Orléans Cedex 2, France.
authors: Dominique
authors: D
authors: Massiot
authors: Conditions Extrêmes et Matériaux: Haute Température et Irradiation, CNRS UPR 3079, 1D Avenue de la Recherche Scientifique, 45071 Orléans Cedex 2, France; Université d'Orléans, Faculté des Sciences, Avenue du Parc Floral, 45067 Orléans Cedex 2, France.
authors: Franck
authors: F
authors: Fayon
keywords: Crystalline fluorides; First principle calculations; Solid state NMR