Organische Chemie I, Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, Universitätsstraße 150, 44801, Bochum, Germany.
Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota, 55455-0431, USA.
Chemistry. 2018 Oct 26;24(60):15983-15987. doi: 10.1002/chem.201803652. Epub 2018 Oct 9.
Motivated by the need to calculate liquid-phase free energies of species and equilibria involving halogen bonding, recent experimental data were used to optimize new Coulomb radii for Br and I for use in the SMD universal solvation model for calculating free energies of solvation. The use of the SMD model with these parameters for Br and I and the SMD values of all other parameters is called SMD18. After parametrization, the SMD18 model was tested for data not used in the parametrization. These data are standard-state free energies (equivalent to equilibrium constants) for 18 ionic equilibria involving Cl, Br, and I halogen bonding in acetonitrile, and the agreement of theory and experiment is satisfactory. The SMD18 model is then used to compare hydrogen bonding to halogen bonding and to reassess the interpretation of recent experiments.
受计算涉及卤素键合的物种和平衡的液相自由能的需求的推动，最近的实验数据被用于优化 Br 和 I 的新库仑半径，以用于 SMD 通用溶剂化模型中计算溶剂化自由能。使用这些参数的 SMD 模型用于 Br 和 I 以及所有其他参数的 SMD 值称为 SMD18。参数化后，对不在参数化中使用的数据测试了 SMD18 模型。这些数据是标准状态自由能（相当于平衡常数），涉及在乙腈中涉及 Cl、Br 和 I 卤素键合的 18 个离子平衡，理论和实验的一致性令人满意。然后，SMD18 模型用于比较氢键和卤素键合，并重新评估最近实验的解释。
