On the unexpected accuracy of the M06L functional in the calculation of 1JFC spin-spin coupling constants

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One-bond spin-spin coupling constants (SSCCs) between F and C are computed with density functional theory (DFT). Surprisingly, M06L stands out for its striking accuracy, outperforming any other investigated functional, including PBE0, otherwise considered one of the most reliable for couplings involving F. Despite the computation of nuclear magnetic resonance (NMR) parameters involving F is known to be a challenging task, even with a rather small basis set as pcJ-1, M06L provides results with a MAD=11.7 Hz, whereas the average deviation gets as much as five times larger for PBE0 (MAD=60.0 Hz). In the context of SSCCs in the order of three hundreds Hertz, this is particularly remarkable. We find that the accuracy of M06L/pcJ-1 in predicting 1JFC constants does not stem from a well-suited exchange or correlation part of the functional. Instead, it is believed to arise from a fortuitous cancellation of errors, as revealed by investigating the convergence of the basis set. Our findings also indicate that 1JFC constants are highly dependent on the amount of exact exchange included in the expression of the functional, with large fractions being critically important to achieve satisfactory results. Studying the effects of the geometry on 1JFC, we find that optimizing the geometry at the level of theory used to calculate SSCCs generally improves the quality of the results, although the combination of a M06-2X/aug-cc-pVTZ geometry with M06L/pcJ-1 1JFC constants best reproduces the experimental data for organofluorine compounds (with the exception of fluoroalkenes).
Original languageEnglish
JournalJournal of Chemical Theory and Computation
ISSN1549-9618
Publication statusAccepted/In press - 21 Sep 2021

    Research areas

  • Faculty of Science - NMR, Spin-spin coupling constant, density functional theory (DFT), fluorine chemistry

ID: 280173806