Quantifying London dispersion effects through novel local correlation techniques

在第一个创始阶段，我们在基于区域的局域对自然轨道耦合团簇(DLPNO-CCSD(T))框架内开发了一个能量分解方案，该方案允许将精确的DLPNO-CCSD(T)能量合理地分解成具有化学意义的相加贡献。这种方法也被称为“局部能量分解”(LED)分析，可以用来量化任意数量的碎片或分子之间相互作用能量中难以捉摸的伦敦色散分量。这一计划的挑战性应用将在第二个资助期进行，最终目的是有助于合理控制伦敦弥散对化学反应的影响。这些应用将与几个实验小组合作进行，包括：(I)复杂的有机催化反应；(Ii)用于量化溶液中伦敦分散效应的分子平衡；(Iii)有机金属化学中配位键的研究。此外，LED分析的进一步发展将在第二个资助期进行。特别是，我们将在ORCA代码中实现该方案的开放外壳版本，这将允许极大地增加可研究的系统数量。此外，一系列简单而强大的工具也将在ORCA中实现，用于LED分析的不同组件的空间分析。

During the first founding period, we developed an energy decomposition scheme within the domain-based local pair natural orbital coupled-cluster (DLPNO-CCSD(T) framework, which allows for a physically sound decomposition of the accurate DLPNO-CCSD(T) energy into additive, chemically meaningful contributions. This method, also called "Local Energy Decomposition" (LED) analysis, can be used for quantifying the elusive London dispersion component of the interaction energy between an arbitrary number of fragments or molecules. Challenging applications of this scheme will be carried out during the second funding period, with the final aim of contributing to the rational control of London dispersion effects on chemical reactivity. These applications will be carried out in collaboration with several experimental groups and include: (i) complex organocatalyzed reactions; (ii) molecular balances for the quantification of London dispersion effects in solution; (iii) the study of the coordination bond in organometallic chemistry. Moreover, further developments of the LED analysis will be carried out during the second funding period. In particular, we will implement in the ORCA code an open-shell version of this scheme that will allow for a tremendous increase on the number of systems that can be studied. In addition, a series of simple yet powerful tools for the spatial analysis of the different components of the LED analysis will be also implemented in ORCA.