Advances in the computation of nmr parameters for inorganic nuclides

Abstract

In this article, we discuss practical aspects of the computation of NMR parameters of inorganic nuclides, as well as insights afforded by such calculations into the characterization of molecular-level structure and dynamics and the validation of theoretical models. An emphasis is placed on calculation of the magnetic shielding tensors of solids using cluster-based models that account for intermolecular interactions. In particular, the use of valence modification of terminal atoms using bond valence theory (VMTA/BV), which reduces net charges on clusters through terminal pseudoatoms with nonstandard nuclear charges, is demonstrated to be a robust technique for calculations on nuclei in network solids. Cluster-based calculations, including those that employ the VMTA/BV method, afford a unique opportunity to calculate magnetic shielding tensors for nuclei in solids by using density functional theory approximations beyond the generalized gradient approximation and by incorporating relativistic effects at the spin-orbit level. These developments are spurred by use of the zeroth-order regular approximation (ZORA), which provides a robust method of accounting for relativistic effects (up to the spin-orbit level) experienced by valence electrons. Calculations of NMR parameters are discussed for fluorine, cadmium, tin, tellurium, mercury, lead, and platinum, all of which have seen significant advances in recent years. These examples highlight the importance of such factors as coordination geometry, oxidation state, relativistic effects, and density functional approximations on computed magnetic shielding tensors.