NMR interaction tensors of 51V and 207Pb in vanadinite, Pb5(VO4)3Cl, determined from DFT calculations and single-crystal NMR measurements, using only one general rotation axis

Abstract

Orientation-dependent NMR spectra of a single crystal of the mineral vanadinite, Pb₅(VO₄)₃Cl, were acquired using only one rotation axis with a general orientation in the hexagonal crystal lattice (space group P6₃/m). The chemical shift (CS) tensors for the ²⁰⁷Pb on Wyckoff positions 6h and 4f, and both CS and quadrupole coupling tensor Q for ⁵¹V at the positions 6h were determined by including the NMR response of symmetry-related atoms in the unit cell (and in case of ²⁰⁷Pb at 4f, also the isotropic shift from MAS NMR spectra). This previously suggested 'single rotation method' greatly reduces the necessary amount of data acquisition and analysis. The precise orientation of the rotation axis could not be found by X-ray diffraction experiments because of the high linear absorption coefficient of vanadinite, which is chiefly due to its high lead content. The axis orientation was therefore included into the multi-parameter data fit routine. This NMR-based approach is widely applicable, and offers an alternative way of orienting single crystals. The NMR parameters derived from the tensor eigenvalues are δ_iso=(-1729±9) ppm, Δδ=(-1071±5) ppm, η_CS=0.362±0.008 for ²⁰⁷Pb at positions 6h, and δ_iso=(-1619±2) ppm, Δδ=(-780±58) ppm, η_CS=0.06±0.08 for positions 4f. For ⁵¹V, δ_iso=(-509±3) ppm, Δδ=(-37±2) ppm, η_CS=0.78±0.09, with the quadrupolar coupling described by χ=(2.52±0.01) MHz and η_Q=0.047±0.003. In contrast to the precisely determined tensor eigenvalues, the orientation of the eigenvectors in the crystal ab -plane of the vanadinite system could only be resolved by resorting to data obtained from density functional theory (DFT) calculations.

Keywords: (207)Pb chemical shift tensor; (51)V chemical shift and quadrupolar coupling tensor; Single-crystal NMR; Vanadinite.