title: Spin-orbit effects on the (119)Sn magnetic-shielding tensor in solids: a ZORA/DFT investigation.
abstract: Periodic-boundary and cluster calculations of the magnetic-shielding tensors of (119)Sn 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.
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, USA. alkan@udel.edu dybowski@udel.edu.
authors.forename: Fahri
authors.initials: F
authors.lastname: Alkan
authors.forename: Sean T
authors.initials: ST
authors.lastname: Holmes
authors.forename: Robbie J
authors.initials: RJ
authors.lastname: Iuliucci
authors.forename: Karl T
authors.initials: KT
authors.lastname: Mueller
authors.forename: Cecil
authors.initials: C
authors.lastname: Dybowski