title: How reliable are GIAO calculations of 1H and 13C NMR chemical shifts? A statistical analysis and empirical corrections at DFT (PBE/3z) level.
abstract: 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/3ζ) - 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 δC,calc) ± 6.05 ppm for (13)C.
authors.affiliation: Institute of Organic Chemistry of Ufa Scientific Centre of Russian Academy of Sciences, Russia, 450054, Ufa, Prospekt Oktyabrya, 71. evgeniy@pankratyev.com
authors.forename: Evgeniy Yu
authors.initials: EY
authors.lastname: Pankratyev
authors.forename: Artur R
authors.initials: AR
authors.lastname: Tulyabaev
authors.forename: Leonard M
authors.initials: LM
authors.lastname: Khalilov