First-Principle Predictions of Absolute pKa's of Organic Acids in Dimethyl Sulfoxide Solution
- 31 December 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (3) , 814-822
- https://doi.org/10.1021/ja0378097
Abstract
MP2/6-311++G(d,p) and B3LYP/6-311++G(2df,p) methods were found to be able to predict the gas-phase acidities of various organic acids with a precision of 2.2 and 2.3 kcal/mol. A PCM cluster-continuum solvation method was developed that could predict the solvation free energies of various neutral, cationic, and anionic organic species in DMSO with a precision of about 2.0 kcal/mol. Using these carefully tested methods, we successfully predicted the pKa's of 105 organic acids in DMSO with a precision of 1.7−1.8 pKa units. We also predicted the pKa's of a variety of organosilanes in DMSO for the first time using the newly developed methods. This study was one of the first that employed first-principle methods for calculating pKa's of unrelated compounds in organic solutions.Keywords
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