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Analysis of the bond‐valence method for calculating 29 Si and 31 P magnetic shielding in covalent network solids
Author(s) -
Holmes Sean T.,
Alkan Fahri,
Iuliucci Robbie J.,
Mueller Karl T.,
Dybowski Cecil
Publication year - 2016
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24389
Subject(s) - electromagnetic shielding , valence (chemistry) , covalent bond , chemistry , cluster (spacecraft) , density functional theory , valence electron , shielding effect , atomic physics , electron , computational chemistry , materials science , physics , quantum mechanics , organic chemistry , computer science , composite material , programming language
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.