In the present study, we tested the widely used density functionals BP86, PBE, OLYP, TPSS, M06-L, B3LYP, PBE0, mPW1PW, B97, BHandHLYP, TPSS0, M06, M06-2X, CAM-B3LYP, ωB97x, and B2PLYP with the cc-pCVQZ basis set in calculations on a set of 23 nitroxide radicals with well-resolved 14N anisotropic hyperfine coupling (HFC) constants. The results were compared with those obtained using the B3LYP/N07D and PBE/N07D methods. The convergence of the HFC values to the complete basis set limit is briefly discussed. The best results were obtained using the M06/COSMO method, with a mean absolute deviation (MAD) of 0.4 G for the dipole–dipole contribution and MAD = 0.6 G for the contact coupling contribution (as compared to 1.1 G and 1.0 G, respectively, for the B3LYP/N07D/COSMO method and 1.7 G and 0.5 G, respectively, for the B3LYP/N07D method). The majority of the functionals yielded satisfactory results for the dipole–dipole contribution, but only the M06 functional yielded similar errors for both the dipole–dipole and isotropic contributions. The RIJCOSX and RI approximations introduced errors equal to or smaller than 0.01 G.
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The research was partially supported by the Russian Science Foundation (ENG, grant 14-33-00017) and the Russian Foundation for Basic Research (OIG, grant 18-33-00866 mol_a). Calculations were performed using resources of the Supercomputing Center of the Lomonosov Moscow State University .
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