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How reliable are GIAO calculations of 1 H and 13 C NMR chemical shifts? A statistical analysis and empirical corrections at DFT (PBE/3z) level
Author(s) -
Pankratyev Evgeniy Yu.,
Tulyabaev Artur R.,
Khalilov Leonard M.
Publication year - 2011
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.21786
Subject(s) - chemical shift , chemistry , computational chemistry , carbon 13 nmr , confidence interval , density functional theory , mathematics , statistics , stereochemistry
Reliability of calculated 1 H and 13 C NMR chemical shifts for various classes of organic compounds obtained with gauge‐invariant atomic orbital (GIAO) approach has been studied at the PBE/3ζ level (as implemented in PRIRODA code) using linear regression analysis with experimental data. Empirical corrections for the calculated chemical shifts δ H,calc = δ PBE/ 3 ζ − 0.08 ppm (RMS 0.18 ppm, MAD 0.66 ppm) and δ C,calc = δ PBE/ 3 ζ − 6.35 ppm (RMS 3.09 ppm, MAD 9.42 ppm) have been developed using the sets of 263 and 308 experimental values for 1 H and 13 C chemical shifts, respectively. The confidence intervals of NMR chemical shifts at 95% confidence probability are δ H,calc ± 0.35 ppm for 1 H and δ C,calc ± 6.05 ppm for 13 C. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011