Pollice Robert, Fleckenstein Felix, Shenderovich Ilya, Chen Peter
ETH Zürich, Laboratorium für Organische Chemie, Vladimir-Prelog-Weg 2, HCI G207/ETH Zürich, Zürich, 8093, Switzerland.
Universität Regensburg, Fakultät für Chemie und Pharmazie, Universitätsstraße 31, Regensburg, 93040, Germany.
Angew Chem Int Ed Engl. 2019 Oct 1;58(40):14281-14288. doi: 10.1002/anie.201905436. Epub 2019 Aug 30.
The importance of London dispersion for structure and stability of molecules with less than about 200 atoms has been established in recent years but the quantitative understanding is still largely based on computations because of a persistent lack of suitable experimental data. We herein report a comprehensive computational and experimental study of the compensation of London dispersion in proton-bound dimer dissociations showing that total compensation is largely invariant in both polar and nonpolar aprotic solvents spanning a wide range of bulk polarizabilities. Additionally, we find that compensation by solvent (which is about 40-80 %) largely dominates over compensation in the gas phase (which is about 0-40 %) for typical experimental temperatures.
近年来，伦敦色散力对原子数少于约200个的分子的结构和稳定性的重要性已得到证实，但由于一直缺乏合适的实验数据，定量理解仍主要基于计算。我们在此报告了一项关于质子键合二聚体解离中伦敦色散力补偿的全面计算和实验研究，结果表明，在具有广泛体极化率的极性和非极性非质子溶剂中，总补偿在很大程度上是不变的。此外，我们发现，在典型实验温度下，溶剂的补偿（约40 - 80%）在很大程度上超过气相中的补偿（约0 - 40%）。
