NMR parameters in alkali, alkaline earth and rare earth fluorides from first principle calculations

Abstract

19F isotropic chemical shifts for alkali, alkaline earth and rare earth of column 3 basic fluorides are measured and the corresponding isotropic chemical shieldings are calculated using the GIPAW method. When using PBE exchange correlation functional for the treatment of the cationic localized empty orbitals of Ca2+, Sc3+ (3d) and La3+ (4f), a correction is needed to accurately calculate 19F chemical shieldings. We show that the correlation between experimental isotropic chemical shifts and calculated isotropic chemical shieldings established for the studied compounds allows to predict 19F NMR spectra of crystalline compounds with a relatively good accuracy. In addition, we experimentally determine the quadrupolar parameters of 25Mg in MgF2 and calculate the electric field gradient of 25Mg in MgF2 and 139La in LaF3 using both PAW and LAPW methods. The orientation of the EFG components in the crystallographic frame, provided by DFT calculations, is analysed in term of electron densities. It is shown that consideration of the quadrupolar charge deformation is essential for the analysis of slightly distorted environments or highly irregular polyhedra.

18 pages, 8 figures, 4 tables and ESI

References in corpus (5)

• All-electron magnetic response with pseudopotentials: NMR chemical shifts
• A First Principles Theory of Nuclear Magnetic Resonance J-Coupling in solid-state systems
• A converse approach to the calculation of NMR shielding tensors
• An ab-initio converse NMR approach for pseudopotentials
• DFT investigation of 3d transition metal NMR shielding tensors in diamagnetic systems using the gauge-including projector augmented-wave method

Cited by in corpus (5)

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• The Si-Ge substitutional series in the chiral STW Zeolite Structure Type
• Relativistic nuclear magnetic resonance J-coupling with ultrasoft pseudopotentials and the zeroth-order regular approximation
• NMR shieldings from density functional perturbation theory: GIPAW versus all-electron calculations
• Ultrasoft pseudopotentials with kinetic energy density support: implementing the modified Becke-Johnson potential