Jump to main content
Jump to site search

Issue 28, 2016
Previous Article Next Article

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

Author affiliations

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.

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

Back to tab navigation

Supplementary files

Publication details

The article was received on 01 Jun 2016, accepted on 23 Jun 2016 and first published on 23 Jun 2016


Article type: Paper
DOI: 10.1039/C6CP03807G
Citation: Phys. Chem. Chem. Phys., 2016,18, 18914-18922
  • Open access: Creative Commons BY license
  •   Request permissions

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

    F. Alkan, S. T. Holmes, R. J. Iuliucci, K. T. Mueller and C. Dybowski, Phys. Chem. Chem. Phys., 2016, 18, 18914
    DOI: 10.1039/C6CP03807G

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements