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Journals and Conferences
Two empirically fitted parameters have been derived for 74 levels of theory. They allow fast and reliable pKa calculations using only the Gibbs energy difference between an acid and its conjugated base in aqueous solution (ΔGs(BA)). The parameters were obtained by least-squares fits of ΔGs(BA) vs experimental pKa values for phenols, carboxylic acids, and… (More)
An assessment of multireference character in transition states is considered to be an important component in establishing the expected reliability of various electronic structure methods. In the present work, the multireference characters of the transition states and the forming and breaking of bonds for a large set of hydrogen abstraction reactions from… (More)
Density functional theory calculations, using the SMD continuum model, indicate that hydrogen transfer from totally protonated uric to a tryptophanyl radical in proteins corresponds to a sequential mechanism. Modeling in methyl butanoate indicates that this mechanism is more important in a hydrophobic medium than in water.
π-π stacking interactions do not necessarily change the mechanism involved in the H transfer reaction between phenol and phenoxyl radicals. We propose that, in such cases, the e- is transferred between the π delocalized moieties, while the H+ is transferred between the donor and acceptor atoms.
The results presented in this work demonstrate the high complexity of chemical reactions involving species with multiple acid-base equilibria. For the case study investigated here, it was necessary to consider two radical species for tryptophan (Trp(-H)˙ and Trp˙+) and three fractions for uric acid (H3Ur, H2Ur- and HUr2-) in order to properly reproduce the… (More)