J Chem Phys 2021 Sep;155(11):114304
Department of Chemistry, Mississippi State University, Mississippi State, Mississippi 39762-9573, USA.
This work addresses the pathological behavior of the energetics of dimethyl sulfoxide and related sulfur-containing compounds by providing the computational benchmark energetics of RE species, where R = H/CH and E = O/S, with bent and pyramidal geometries using state-of-the-art methodologies. These 22 geometries were fully characterized with coupled-cluster with single, double, and perturbative triple excitations [CCSD(T)], second-order Møller-Plesset perturbation theory (MP2), and 22 density functional theory (DFT) methods with 8, 12, and 12, respectively, correlation consistent basis sets of double-, triple-, or quadruple-ζ quality. The relative energetics were determined at the MP2 and CCSD(T) complete basis set (CBS) limits using 17 basis sets up to sextuple-ζ and include augmented, tight-d, and core-valence correlation consistent basis sets. Read More