ETH Zürich, Laboratorium für Organische Chemie, Vladimir-Prelog-Weg 2, HCI G207/ETH Zürich, 8093, Zürich, Switzerland.
Angew Chem Int Ed Engl. 2019 Jul 15;58(29):9758-9769. doi: 10.1002/anie.201905439. Epub 2019 Jun 24.
London dispersion, universally attractive forces originating from fluctuating dipoles, is omnipresent in molecules. While its understanding has recently made tremendous progress, its general appreciation is still lagging behind electrostatics. This can be explained by the simple tools available to study electrostatic interactions, such as electrostatic potential (ESP) maps and partial charges, and a lack thereof for dispersion. We herein report a universal quantitative descriptor of dispersion interaction potentials, which allows assessing dispersion visually by London dispersion potential (LDP) maps, and quantitatively using the average LDP on the van der Waals surface. We demonstrate the utility of these new tools by constructing a quantitative dispersion energy scale of the elements and common substituents, studying non-covalent interactions (NCIs), and developing modern linear free energy relationships in catalysis.
伦敦色散力，即源于偶极子波动的普遍吸引力，普遍存在于分子中。尽管人们对它的理解最近取得了巨大的进展，但它的普遍认识仍然落后于静电学。这可以用研究静电相互作用的简单工具来解释，如静电势 (ESP) 图和部分电荷，而缺乏用于色散的工具。我们在此报告了一种通用的色散相互作用势能定量描述符，它允许通过伦敦色散势 (LDP) 图直观地评估色散，以及使用范德华表面上的平均 LDP 进行定量评估。我们通过构建元素和常见取代基的定量色散能标、研究非共价相互作用 (NCIs) 以及开发催化中的现代线性自由能关系来展示这些新工具的实用性。
