Analysis of the bond-valence method for calculating (29) Si and (31) P magnetic shielding in covalent network solids.
(29) Si and (31) P 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 (29) Si and (31) P magnetic-shielding constants. Calculations using the hybrid functional PBE0, in combination with the VMTA/BV approach, result in excellent agreement with experiment. © 2016 Wiley Periodicals, Inc.
Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware, 19716.
Sean T
ST
Holmes
Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware, 19716.
Fahri
F
Alkan
Department of Chemistry, Washington and Jefferson College, Washington, Pennsylvania, 15301.
Robbie J
RJ
Iuliucci
Department of Chemistry, Pennsylvania State University, University Park, Pennsylvania, 16802.|Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington, 99352.
Karl T
KT
Mueller
Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware, 19716.
Cecil
C
Dybowski
DFT; GIPAW; NMR; VMTA/BV; phosphorus; silicon