51V NMR parameters of VOCl3: static and dynamic density functional study from the gas phase to the bulk

Abstract

⁵¹V NMR parameters have been calculated for VOCl₃, the reference compound in ⁵¹V NMR spectroscopy, in order to capture environmental effects in both the neat liquid and the solid state. Using a combination of periodic geometry optimizations and Car–Parrinello molecular dynamics simulations with embedded cluster NMR calculations, we are able to test the ability of current computational approaches to reproduce ⁵¹V NMR properties (isotropic shifts, anisotropic shifts and quadrupole coupling constants) in the gas, liquid and solid states, for direct comparison with liquid and solid-state experimental data. The results suggest that environmental effects in the condensed phases can be well captured by an embedded cluster approach and that the remaining discrepancy with experiment may be due to the approximate density functionals in current use. The predicted gas-to-liquid shift on the isotropic shielding constant is small, validating the common practice to use a single VOCl₃, molecule as reference in ⁵¹V NMR computations.