Quantifying London dispersion effects through novel local correlation techniques

在第一个创建期间，我们在基于域的局部对自然轨道耦合簇（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）能量物理上合理地分解为添加剂，化学上有意义的贡献。这种方法，也称为“局部能量分解”（LED）分析，可用于量化难以捉摸的伦敦色散分量之间的相互作用能量的任意数量的碎片或分子。在第二个资助期内，将对该方案进行初步应用，最终目标是合理控制伦敦色散对化学反应性的影响。这些应用将与几个实验小组合作进行，包括：（一）复杂的有机催化反应;（二）量化溶液中伦敦分散效应的分子平衡;（三）研究有机金属化学中的配位键。此外，LED分析的进一步发展将在第二个资助期内进行。特别是，我们将在ORCA代码中实现该方案的开放式外壳版本，这将使可以研究的系统数量大幅增加。此外，一系列简单而强大的工具，用于LED分析的不同组件的空间分析也将在ORCA中实现。

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.