Chemical-shift tensors of heavy nuclei in network solids: a DFT/ZORA investigation of Pb-207 chemical-shift tensors using the bond-valence method


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Alkan F. , Dybowski C.

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, vol.17, no.38, pp.25014-25026, 2015 (Journal Indexed in SCI) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 17 Issue: 38
  • Publication Date: 2015
  • Doi Number: 10.1039/c5cp03348a
  • Title of Journal : PHYSICAL CHEMISTRY CHEMICAL PHYSICS
  • Page Numbers: pp.25014-25026

Abstract

Cluster models are used in calculation of Pb-207 NMR magnetic-shielding parameters of alpha-PbO, beta-PbO, Pb3O4, Pb2SnO4, PbF2, PbCl2, PbBr2, PbClOH, PbBrOH, PbIOH, PbSiO3, and Pb-3(PO4)(2). We examine the effects of cluster size, method of termination of the cluster, charge on the cluster, introduction of exact exchange, and relativistic effects on calculation of magnetic-shielding tensors with density functional theory. Proper termination of the cluster for a network solid, including approximations such as compensation of charge by the bond-valence (BV) method, is essential to provide results that agree with experiment. The inclusion of relativistic effects at the spin-orbit level for such heavy nuclei is an essential factor in achieving agreement with experiment.