DFT meets the segmented polarization consistent basis sets: Performances in the computation of molecular structures, rotational and vibrational spectroscopic properties

Abstract

Quantum-chemical calculations assist the analysis of laboratory spectra, and often provide the only means to determine spectroscopic data that cannot be accessed experimentally. For the purpose, reliable predictions of structural and spectroscopic parameters are required. Although coupled cluster theory in conjunction with to large basis sets and composite schemes can reach impressive accuracies for structural, thermochemical and spectroscopic properties, it is still limited to small sized molecules. DFT represents the working option for medium to large molecular systems. In this context, systematic investigations are required aimed at characterizing the performances of the different DFT model chemistries. In this work, the accuracy of the popular hybrid B3LYP and the double hybrid B2PLYP functionals coupled to the segmented polarization consistent (aug-)pcs-n basis sets in the prediction of molecular structures and rotational- and vibrational spectroscopic parameters are investigated using a benchmark set of molecules of both atmospheric and astrochemical relevance. For comparison purposes, different flavors of Dunning’s triple-ζ basis sets and the SNSD basis set, are also employed. The convergence behavior of the pcs-n hierarchy with n = 1–4 is also addressed to some extent. The results indicate the B3LYP-D3 functional in conjunction with the aug-pcs-1 or SNSD basis sets as a cost-effective model chemistry for applications in the field of rotational and vibrational spectroscopies. Improved accuracy is obtained by coupling the B2PLYP-D3 functional with the aug-pcs-2 or aug-cc-pVTZ triple-ζ basis sets that show an accuracy around 0.003 Å and 0.3° for bond lengths and angles, 1% and 3% for rotational and quartic centrifugal distortion constants, respectively, 12 cm−1 for fundamental frequencies and 3 km mol−1 for IR intensities. The B2PLYP-D3/maug-cc-pVTZ-dH level keeps the same accuracy, with slightly larger deviations for intensities.