Quantifying London dispersion effects through novel local correlation techniques

在第一个创立期间，我们在基于域的局部对自然轨道耦合簇 (DLPNO-CCSD(T)) 框架内开发了一种能量分解方案，该方案允许将精确的 DLPNO-CCSD(T) 能量在物理上合理分解为附加的、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，可用于量化任意数量的碎片或分子之间相互作用能的难以捉摸的伦敦色散分量。该计划的应用将在第二个资助期内进行，最终目标是与多个实验小组合作进行，包括：（i）复杂的有机催化反应；（ii）溶液中伦敦色散效应的定量研究；（iii）有机金属化学中的配位键的研究。在 ORCA 代码中实现该方案的开放外壳版本，这将大大增加可研究的系统数量。此外，ORCA 中还将实现一系列简单但功能强大的工具，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.