Frömbgen Tom, Drysch Katrin, Zaby Paul, Dölz Jürgen, Ingenmey Johannes, Kirchner Barbara
Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstraße 4 + 6, Bonn D-53115, Germany.
Max-Planck-Institut Für Chemische Energiekonversion, Stiftstrasse 34-36, Mülheim an der Ruhr D-45470, Germany.
J Chem Theory Comput. 2024 Mar 12;20(5):1838-1846. doi: 10.1021/acs.jctc.3c00799. Epub 2024 Feb 19.
In this work, we present a new theory to treat multicomponent liquids based on quantum-chemically calculated clusters. The starting point is the binary quantum cluster equilibrium theory, which is able to treat binary systems. The theory provides one equation with two unknowns. In order to obtain another linearly independent equation, the conservation of mass is used. However, increasing the number of components leads to more unknowns, and this requires linearly independent equations. We address this challenge by introducing a generalization of the conservation of arbitrary quantities accompanied by a comprehensive mathematical proof. Furthermore, a case study for the application of the new theory to ternary mixtures of chloroform, methanol, and water is presented. Calculated enthalpies of vaporization for the whole composition range are given, and the populations or weights of the different clusters are visualized.
在这项工作中，我们提出了一种基于量子化学计算团簇来处理多组分液体的新理论。起点是二元量子团簇平衡理论，它能够处理二元体系。该理论提供了一个含有两个未知数的方程。为了得到另一个线性独立方程，我们使用了质量守恒。然而，增加组分数会导致更多未知数，这就需要线性独立方程。我们通过引入任意量守恒的推广并给出全面的数学证明来应对这一挑战。此外，还给出了新理论应用于氯仿、甲醇和水三元混合物的案例研究。给出了整个组成范围内计算得到的汽化焓，并可视化了不同团簇的数量或权重。
