title: First-principle predictions of absolute pKa's of organic acids in dimethyl sulfoxide solution.
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.
authors.affiliation: Department of Chemistry, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Yao
authors.initials: Y
authors.lastname: Fu
authors.forename: Lei
authors.initials: L
authors.lastname: Liu
authors.forename: Rui-Qiong
authors.initials: RQ
authors.lastname: Li
authors.forename: Rui
authors.initials: R
authors.lastname: Liu
authors.forename: Qing-Xiang
authors.initials: QX
authors.lastname: Guo