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

Fahri Alkan, Sean T. Holmes, Robbie J. Iuliucci, Karl T. Mueller, Cecil Dybowski

Research output: Contribution to journalArticle

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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.

Original languageEnglish (US)
Pages (from-to)18914-18922
Number of pages9
JournalPhysical Chemistry Chemical Physics
Volume18
Issue number28
DOIs
StatePublished - Jan 1 2016

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All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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