Smiatek Jens
Institut für Computerphysik, Universität Stuttgart, Allmandring 3, D-70569 Stuttgart, Germany.
J Chem Phys. 2019 May 7;150(17):174112. doi: 10.1063/1.5092567.
We present a theoretical and numerical framework for the study of molecular attraction mechanisms between species in solution. The respective approach provides detailed insight into the enthalpic contributions of solvation and relies on molecular exchange reactions in combination with electronic perturbations. Associated values for chemical reactivity indices such as the electronegativity, the chemical hardness, and the electrophilicity are obtained from straightforward conceptual density functional theory calculations. Further analysis of corresponding reaction energies allows us to estimate the enthalpic stability of solvent-solute, solvent-ion, and ion-ion complexes. The validity of our approach is demonstrated by the calculation of donor numbers for distinct solvents. Our results reveal a reasonable agreement between calculated and experimental outcomes which highlights the applicability of our combined theoretical and computational approach.
我们提出了一个用于研究溶液中物种间分子吸引机制的理论和数值框架。相应的方法深入洞察了溶剂化的焓贡献，并依赖于分子交换反应与电子微扰相结合。诸如电负性、化学硬度和亲电性等化学反应性指数的相关值，是通过直接的概念密度泛函理论计算获得的。对相应反应能量的进一步分析使我们能够估计溶剂 - 溶质、溶剂 - 离子和离子 - 离子络合物的焓稳定性。通过计算不同溶剂的给体数，证明了我们方法的有效性。我们的结果显示计算结果与实验结果之间有合理的一致性，这突出了我们理论与计算相结合方法的适用性。
