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H 2 O, H 2 , HF, F 2 and F 2 O nuclear magnetic shielding constants and indirect nuclear spin–spin coupling constants (SSCCs) in the BHandH/pcJ‐ n and BHandH/XZP Kohn–Sham limits
Author(s) -
Kupka Teobald
Publication year - 2009
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.2500
Subject(s) - chemistry , extrapolation , basis set , coupling constant , basis (linear algebra) , electromagnetic shielding , isotropy , ab initio , ab initio quantum chemistry methods , computational chemistry , atomic physics , density functional theory , molecule , physics , quantum mechanics , mathematical analysis , mathematics , geometry , organic chemistry
Abstract Good performance of segmented contracted basis sets XZP, where X = D, T, Q and 5, for obtaining H 2 O, H 2 , HF, F 2 and F 2 O nuclear isotropic shielding constants in the BHandH Kohn–Sham basis set limit was shown. The results of two‐ and three‐parameter complete basis set limit extrapolation schemes were compared with experimental results, earlier literature data and benchmark ab initio results. Similar convergence patterns of shieldings obtained from calculations using general purpose XZP basis sets and from polarization‐consistent basis sets pcS‐ n and pcJ‐ n , where n = 0, 1, 2, 3 and 4, designed to accurately predict magnetic properties were observed. On the contrary, the SSCCs were more sensitive to the XZP basis set size and generally less accurate than those estimated using pcJ‐ n basis set family. The BHandH density functional markedly outperforms B3LYP method in predicting heavy atom shieldings and SSCCs values in the studied systems. Copyright © 2009 John Wiley & Sons, Ltd.