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

作者：Holmes Sean T; Alkan Fahri; Iuliucci Robbie J; Mueller Karl T; Dybowski Cecil

来源：Journal of Computational Chemistry, 2016, 37(18): 1704-1710.

DOI：10.1002/jcc.24389

• NMR
• silicon
• phosphorus
• DFT
• VMTA/BV
• GIPAW

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.

• 出版日期2016-7-5