A simple computational approach for pKa calculation of organosulfur compounds
DOI:
https://doi.org/10.2298/JSC200518042AKeywords:
DFT method, Diffuse function basis set, DMSO solventAbstract
The present work is related to predicting the pKa values of organosulfur compounds through Density Functional Theory (DFT). In this study 22 organosulfur compounds have been considered to calculate theoretical pKa values. Main emphasis has been given on the substitution of different groups on the Sulfur atom. The computations were performed in the presence of Dimethyl sulfoxide (DMSO) as solvent. Experimentally the order of increase of acidity is; Sulfides <
< Sulfoxides < Sulfones. Our computed pKa values also follow the same order. The theoretical pKa values are computed using the DFT method B3LYP, with the basis sets 6-31G(d), 6-31+G(d,p) and IEFPCM bulk solvation model. The majority of computed pKa values are in excellent agreement with the experimental ones through the diffuse function basis set. Hence this computational approach, B3LYP/6-31+G(d,p)/IEFPCM, could be utilized to predict the pKa values of these types of organosulfur compounds.
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