Analysis of the bond-valence method for calculating 29Si and 31P magnetic shielding in covalent network solids

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

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

Abstract

29Si and 31P magnetic-shielding tensors in covalent network solids have been evaluated using periodic and cluster-based calculations. The cluster-based computational methodology employs pseudoatoms to reduce the net charge (resulting from missing co-ordination on the terminal atoms) through valence modification of terminal atoms using bond-valence theory (VMTA/BV). The magnetic-shielding tensors computed with the VMTA/BV method are compared to magnetic-shielding tensors determined with the periodic GIPAW approach. The cluster-based all-electron calculations agree with experiment better than the GIPAW calculations, particularly for predicting absolute magnetic shielding and for predicting chemical shifts. The performance of the DFT functionals CA-PZ, PW91, PBE, rPBE, PBEsol, WC, and PBE0 are assessed for the prediction of 29Si and 31P magnetic-shielding constants. Calculations using the hybrid functional PBE0, in combination with the VMTA/BV approach, result in excellent agreement with experiment.

Original languageEnglish (US)
Pages (from-to)1704-1710
Number of pages7
JournalJournal of Computational Chemistry
DOIs
StatePublished - Jul 5 2016

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Computational Mathematics

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