Analysis of the Bond-Valence Method for Calculating Si-29 and P-31 Magnetic Shielding in Covalent Network Solids


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

JOURNAL OF COMPUTATIONAL CHEMISTRY, vol.37, no.18, pp.1704-1710, 2016 (Journal Indexed in SCI) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 37 Issue: 18
  • Publication Date: 2016
  • Doi Number: 10.1002/jcc.24389
  • Title of Journal : JOURNAL OF COMPUTATIONAL CHEMISTRY
  • Page Numbers: pp.1704-1710
  • Keywords: NMR, silicon, phosphorus, DFT, VMTA/BV, GIPAW, NMR CHEMICAL-SHIFTS, DENSITY-FUNCTIONAL METHODS, CRYSTAL-STRUCTURE, 1ST-PRINCIPLES CALCULATIONS, CALCIUM PHOSPHATES, TIN(II) COMPOUNDS, LOCAL-STRUCTURE, ELECTRON-GAS, HEAVY-NUCLEI, STATE

Abstract

Si-29 and P-31 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 Si-29 and P-31 magnetic-shielding constants. Calculations using the hybrid functional PBE0, in combination with the VMTA/BV approach, result in excellent agreement with experiment. (C) 2016 Wiley Periodicals, Inc.