Minimalist Relativistic Force Field: Prediction of Proton–Proton Coupling Constants in 1H NMR Spectra Is Perfected with NBO Hybridization Parameters

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Molecular properties, Chemical structure, Energy, Molecular structure

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College of Natual Science and Mathematics, Chemistry and Biochemistry


We previously developed a reliable method for multiparametric scaling of Fermi contacts to achieve fast and accurate prediction of proton–proton spin–spin coupling constants (SSCC) in 1H NMR. We now report that utilization of NBO hybridization coefficients for carbon atoms in the involved C–H bonds allows for a significant simplification of this parametric scheme, requiring only four general types of SSCCs: geminal, vicinal, 1,3-, and long-range constants. The method is optimized for inexpensive B3LYP/6-31G(d) molecular geometries. A new DU8 basis set, based on a training set of 475 experimental spin–spin coupling constants, is developed for hydrogen and common non-hydrogen atoms (Li, B, C, N, O, F, Si, P, S, Cl, Se, Br, I) to calculate Fermi contacts. On a test set of 919 SSCCs from a diverse collection of natural products and complex synthetic molecules the method gave excellent accuracy of 0.29 Hz (rmsd) with the maximum unsigned error not exceeding 1 Hz.

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