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

Author(s): Fahri Alkan ¹ ^, ² ^, ³ ^, ⁴ , Sean T. Holmes ¹ ^, ² ^, ³ ^, ⁴ , Robbie J. Iuliucci ⁵ ^, ⁶ ^, ⁷ ^, ⁴ , Karl T. Mueller ⁵ ^, ⁸ ^, ⁹ ^, ⁴ ^, ¹⁰ , Cecil Dybowski ¹ ^, ² ^, ³ ^, ⁴

Publication date (Electronic): 2016

Journal: Physical Chemistry Chemical Physics

Publisher: Royal Society of Chemistry (RSC)

Read this article at

ScienceOpenPublisher PubMed

Bookmark

There is no author summary for this article yet. Authors can add summaries to their articles on ScienceOpen to make them more accessible to a non-specialist audience.

Abstract

Calculations with ZORA/DFT show the importance of spin–orbit coupling on ¹¹⁹Sn magnetic-shielding tensors.

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.