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Published on: March 24, 2019
Spin-orbit effects on the (119)Sn magnetic-shielding tensor in solids: a ZORA/DFT investigation
Fahri Alkan1, Sean T Holmes, Robbie J Iuliucci
1Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, USA. alkan@udel.edu dybowski@udel.edu.
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.
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