DFT calculations of 1H- and 13C-NMR chemical shifts of 3-methyl-1-phenyl-4-(phenyldiazenyl)-1H-pyrazol-5-amine in solution

Geometries of the 3-methyl-1-phenyl-4-(phenyldiazenyl)-1H-pyrazol-5-amine azo-dye compound and its tautomer were optimized using B3LYP and M06-2X functionals in coupling with TZVP and 6-311 + G(d,p) basis sets. The H-1- and C-13-NMR chemical shifts of all species were predicted using 13 density functional theory (DFT) approaches in coupling with TZVP and 6-311 + G(d,p) basis sets at the different optimized geometries by applying the using GIAO method using the eight geometries. The selected functionals are characterized by having different amount of Hartree-Fock exchange. The selected DFT methods were B3LYP, M06-2X, BP86, B97XD, TPSSTPSS, PBE1PBE, CAM-B3LYP, wB97XD, LSDA, HSEH1PBE, PW91PW91, LC-WPBE, and B3PW91. The results obtained were compared with the available experimental data using different statistical descriptors such as root mean square error (RMSE) and maximum absolute error (MAE). Results revealed that the prediction of the H-1-NMR chemical shifts has more significant dependence on the applied geometry than that of the prediction of the C-13-NMR chemical shifts. Among all the examined functionals, B97D and TPSSTPSS functionals were found to be the most accurate ones, while the M06-2X functional is the least accurate one. Results also revealed that the prediction of NMR chemical shifts using TZVP basis sets results is more accurate results than 6-311 + G(2d,p) basis set.

Automated summary

This study investigates the geometries and nuclear magnetic resonance (NMR) chemical shifts of an azo dye compound and its tautomer. The results show that the prediction accuracy is higher for H-1-NMR chemical shifts compared to C-13-NMR chemical shifts. Among the examined methods, B97D and TPSSTPSS are the most accurate, while M06-2X is the least accurate. The use of TZVP basis sets leads to more accurate predictions.