NMR parameters in column 13 metal fluoride compounds (AlF₃, GaF₃, InF₃ and TlF) from first principle calculations

Aymeric Sadoc; Mamata Biswal; Monique Body; Christophe Legein; Florent Boucher; Dominique Massiot; Franck Fayon

doi:10.1016/j.ssnmr.2014.01.001

NMR parameters in column 13 metal fluoride compounds (AlF₃, GaF₃, InF₃ and TlF) from first principle calculations

Solid State Nucl Magn Reson. 2014 May-Jun:59-60:1-7. doi: 10.1016/j.ssnmr.2014.01.001. Epub 2014 Jan 22.

Authors

Aymeric Sadoc¹, Mamata Biswal², Monique Body², Christophe Legein³, Florent Boucher¹, Dominique Massiot⁴, Franck Fayon⁴

Affiliations

¹ Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3, France.
² 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.
³ 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.
⁴ 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.

PMID: 24508247
DOI: 10.1016/j.ssnmr.2014.01.001

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.

Keywords: Crystalline fluorides; First principle calculations; Solid state NMR.

Publication types

Research Support, Non-U.S. Gov't