Spin–orbit effects on the 119Sn magnetic-shielding tensor in solids: a ZORA/DFT investigation

Abstract

Periodic-boundary and cluster calculations of the magnetic-shielding tensors of ¹¹⁹Sn sites in various co-ordination and stereochemical environments are reported. The results indicate a significant difference between the predicted NMR chemical shifts for tin(II) sites that exhibit stereochemically-active lone pairs and tin(IV) sites that do not have stereochemically-active lone pairs. The predicted magnetic shieldings determined either with the cluster model treated with the ZORA/Scalar Hamiltonian or with the GIPAW formalism are dependent on the oxidation state and the co-ordination geometry of the tin atom. The inclusion of relativistic effects at the spin–orbit level removes systematic differences in computed magnetic-shielding parameters between tin sites of differing stereochemistries, and brings computed NMR shielding parameters into significant agreement with experimentally-determined chemical-shift principal values. Slight improvement in agreement with experiment is noted in calculations using hybrid exchange–correlation functionals.