How Reliable are GIAO Calculations of 1H and 13C NMR Chemical Shifts? A Statistical Analysis and Empirical Corrections at DFT (PBE/3z) Level
How Reliable are GIAO Calculations of 1H and 13C NMR Chemical Shifts? A Statistical Analysis and Empirical Corrections at DFT (PBE/3z) Level
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DOI：
10.1002/jcc.21786
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发表时间：
2011-07-15
影响因子：
3
通讯作者：
Khalilov, Leonard M.
中科院分区：
文献类型：
--
作者：
Pankratyev, Evgeniy Yu.;Tulyabaev, Artur R.;Khalilov, Leonard M.
在PBE/3 zeta水平上（如在PRIRODA程序中实现的），用线性回归分析方法研究了用规范不变原子轨道（GIAO）方法计算的各类有机化合物的H-1和C-13 NMR化学位移的可靠性。计算的化学位移的经验校正δ（H，calc）= δ（PBE/3 zeta）- 0.08 ppm（RMS 0.18 ppm，MAD 0.66 ppm）和delta（C，计算值）= delta（PBE/3 zeta）- 6.35 ppm（RMS 3.09 ppm，MAD 9.42 ppm）已开发使用的H-1和C-13化学位移的263和308实验值分别。在95%置信概率下，NMR化学位移的置信区间为H-1的δ（H，计算值）+/- 0.35 ppm和C-13的δ（C，计算值）+/- 6.05 ppm。(C)2011 Wiley Periodicals，Inc. J Comput Chem 32：1993-1997，2011
Reliability of calculated H-1 and C-13 NMR chemical shifts for various classes of organic compounds obtained with gauge-invariant atomic orbital (GIAO) approach has been studied at the PBE/3 zeta level (as implemented in PRIRODA code) using linear regression analysis with experimental data. Empirical corrections for the calculated chemical shifts delta(H,calc) = delta(PBE/3 zeta) - 0.08 ppm (RMS 0.18 ppm, MAD 0.66 ppm) and delta(C,calc) = delta(PBE/3 zeta) - 6.35 ppm (RMS 3.09 ppm, MAD 9.42 ppm) have been developed using the sets of 263 and 308 experimental values for H-1 and C-13 chemical shifts, respectively. The confidence intervals of NMR chemical shifts at 95% confidence probability are delta(H,calc) +/- 0.35 ppm for H-1 and delta(C,calc) +/- 6.05 ppm for C-13. (C) 2011 Wiley Periodicals, Inc. J Comput Chem 32: 1993-1997, 2011