Modeling of London Dispersion Interactions in Molecular Chemistry

伦敦色散相互作用的准确帐户和现代量子化学方法的“化学”分析是这个项目的中心主题。基于我们对色散校正平均场（DFT-D/NL）方法的洞察力和经验，我们将继续通过三个领域的项目对分子系统中伦敦色散相互作用的透彻理解和量化做出贡献：方法开发，与其他参与者在理论上困难或非标准情况下的联合应用和支持。具体而言，将审议以下专题：- 通过一种新的、单独开发的复合程序，基于稳健和精确的紧束缚量子化学方法和新的分子间力场，自动生成构象系综和簇结构，即使对于大型系统，-溶液中的分子热化学和反应势垒和机制的计算，重点是分散控制，-非共价相互作用的能量分解分析，以揭示分散的重要性，特别是关于分散能量供体（DED）与反DED（去稳定化）行为，- 包括多体弥散效应的D4模型的进一步发展-非-局域VV 10密度泛函与激发态量子化学方法和解释实验涉及电子激发特别注意将支付的影响分散的化学性质的兴趣。使用所应用的色散校正密度泛函方法，这在技术上和概念上是容易实现的，因为电子和色散能量被假设为是加性的，并且校正可以容易地打开/关闭。此外，建议的D4模型（与D3相比）将允许调查特别是金属系统的色散效应的电荷依赖性，以及更准确地考虑多体色散能。新DFT-D4方法的更高准确度与改进的采样技术相结合，将导致治疗的整体可靠性显著提高。

The accurate account of London dispersion interactions and their 'chemical' analysis by modern quantum chemical methods are the central themes of this project. Based on our insight and experience with dispersion corrected mean-field (DFT-D/NL) methods we will continue to contribute to gaining a thorough understanding and quantification of London dispersion interactions in molecular systems with projects in the three areas: method development, joint applications with and support of other participants in theoretically difficult or non standard cases. In detail, the following topics will be considered:- automatic generation of conformation ensembles and cluster structures even for large systems by a new, separately developed composite procedure based on a robust and accurate tight-binding quantum chemical method and the new intermolecular force field,- molecular thermochemistry in solution and computation of reaction barriers and mechanisms with an emphasis on dispersion control,- energy decomposition analysis of non-covalent interactions to reveal the importance of dispersion in particular regarding dispersion energy donor (DED) vs. anti-DED (de-stabilising) behavior,- further development of the D4 model including many-body dispersion effects- coupling of the non-local VV10 density functional with excited state quantum chemistry methods and interpretation of experiments involving electronic excitationParticular attention will be paid to the effect of dispersion on the chemical property of interest. With the applied dispersion corrected density functional methods this is technically and conceptually easily possible because the electronic and dispersion energies are assumed to be additive and the correction can easily be switched on/off. In addition the proposed D4 model (in comparison to D3) will allow to investigate the charge dependence of dispersion effects in particular for metallic systems as well as a more accurate consideration of the many-body dispersion energy. The higher accuracy of the new DFT-D4 methods in combination with improved sampling techniques will lead to overall significantly increased reliability of the treatments.