title: Toward Prediction of the Chemistry in Ionic Liquids: An Accurate Computation of Absolute pK(a) Values of Benzoic Acids and Benzenethiols.
abstract: In contrast to the great success of computational methodologies in molecular solvents, effective and accurate calculation of the fundamental bond energetic properties in ionic liquids (ILs) is essentially absent. This is largely due to the unusual complexity of handling solvation quantities of ILs and the lack of precisely determined bond parameters to serve as the authentic benchmark to calibrate the modeling methodology. Herein, we report the first accurate calculations of absolute pK(a) values in a commonly used IL, [Bmim][NTf2], with the carefully developed "ion-biased" cluster-continuum model. Experimental pK(a) values of benzoic acids and benzenethiols in [Bmim][NTf2] were reproduced with mean unsigned errors of only 0.3 and 0.5 pK(a) units, respectively, which enables theoretical approaches with a suitable strategy as a powerful tool to handle complicated problems in ILs and to eventually realize the rational design of the IL chemistry.
authors: State Key Laboratory of Elemento-organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University , Tianjin 300071, China.
authors: Xiao-Song
authors: XS
authors: Xue
authors: State Key Laboratory of Elemento-organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University , Tianjin 300071, China.
authors: Ya
authors: Y
authors: Wang
authors: State Key Laboratory of Elemento-organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University , Tianjin 300071, China.
authors: Chen
authors: C
authors: Yang
authors: Center of Basic Molecular Science, Department of Chemistry, Tsinghua University , Beijing 100084, China.
authors: Pengju
authors: P
authors: Ji
authors: State Key Laboratory of Elemento-organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University , Tianjin 300071, China.|Center of Basic Molecular Science, Department of Chemistry, Tsinghua University , Beijing 100084, China.
authors: Jin-Pei
authors: JP
authors: Cheng