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


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Alkan F. , Holmes S. T. , Iuliucci R. J. , Mueller K. T. , Dybowski C.

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, vol.18, no.28, pp.18914-18922, 2016 (Journal Indexed in SCI) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 18 Issue: 28
  • Publication Date: 2016
  • Doi Number: 10.1039/c6cp03807g
  • Title of Journal : PHYSICAL CHEMISTRY CHEMICAL PHYSICS
  • Page Numbers: pp.18914-18922

Abstract

Periodic-boundary and cluster calculations of the magnetic-shielding tensors of Sn-119 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 exchangecorrelation functionals.