Computational NMR coupling constants: Shifting and scaling factors for evaluating <inf>1</inf>J<inf>CH</inf>

J. San Fabián, J. M. García De La Vega, R. Suardíaz, M. Fernández-Oliva, C. Pérez, R. Crespo-Otero, R. H. Contreras

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Abstract

Optimized shifting and/or scaling factors for calculating one-bond carbon-hydrogen spin-spin coupling constants have been determined for 35 combinations of representative functionals (PBE, B3LYP, B3P86, B97-2 and M06-L) and basis sets (TZVP, HIII-su3, EPR-III, aug-cc-pVTZ-J, ccJ-pVDZ, ccJ-pVTZ, ccJ-pVQZ, pcJ-2 and pcJ-3) using 68 organic molecular systems with 88 1JCH couplings including different types of hybridized carbon atoms. Density functional theory assessment for the determination of 1JCH coupling constants is examined, comparing the computed and experimental values. The use of shifting constants for obtaining the calculated coupling improves substantially the results, and most models become qualitatively similar. Thus, for the whole set of couplings and for all approaches excluding those using the M06 functional, the root-mean-square deviations lie between 4.7 and 16.4 Hz and are reduced to 4-6.5 Hz when shifting constants are considered. Alternatively, when a specific rovibrational contribution of 5 Hz is subtracted from the experimental values, good results are obtained with PBE, B3P86 and B97-2 functionals in combination with HIII-su3, aug-cc-pVTZ-J and pcJ-2 basis sets. Copyright © 2013 John Wiley & Sons, Ltd.
Original languageEnglish
Pages (from-to)775-787
JournalMagnetic Resonance in Chemistry
Volume51
Issue number12
DOIs
Publication statusPublished - 1 Dec 2013

Keywords

  • basis sets
  • coupling constants
  • density functional
  • NMR spectroscopy

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    San Fabián, J., García De La Vega, J. M., Suardíaz, R., Fernández-Oliva, M., Pérez, C., Crespo-Otero, R., & Contreras, R. H. (2013). Computational NMR coupling constants: Shifting and scaling factors for evaluating <inf>1</inf>J<inf>CH</inf> Magnetic Resonance in Chemistry, 51(12), 775-787. https://doi.org/10.1002/mrc.4014