费米和库仑关联对相互作用量子原子能量分配的影响
Fermi and Coulomb correlation effects upon the interacting quantum atoms energy partition
摘要：
相互作用量子原子（IQA）电子能量分配是量子化学拓扑学中的一个重要方法，它对物理化学中不同体系和过程的研究具有重要意义。已经有几次尝试在IQA方法中包括电子相关（EC），例如，通过DFT和Hartree-Fock/耦合簇（HF/CC）跃迁密度。本文通过考虑自旋相关的单电子和双电子矩阵$D^{\mathrm{HF/CC}}_{pσq σ}$和$d^{\mathrm{HF/CC}}_{pσqσrτsτ}$，解决了费米和库仑关联中EC的分离及其对IQA分析的影响，其中$σ$和$τ$分别代表$α$和$β$自旋投影。我们通过考虑BeH $_2$，BH，CN $^-$，HF，LiF，NO $^+$，LiH，H $_2$ O $\cdots$ H $_2$ O和C $_2$ H $_2$来说明这种方法，它们包括非极性共价，极性共价，离子和氢键系统。相同和不同的自旋贡献（$i$）的净，相互作用和交换相关IQA能量分量和（$ii$）定义在分子中的原子的量子理论的离域指数仔细检查和讨论。总体而言，我们预计这种分析将产生重要的见解费米和库仑相关的共价键，分子间相互作用和电子离域在物理化学。
英文摘要：
The Interacting Quantum Atoms (IQA) electronic energy partition is an important method in the field of quantum chemical topology which has given important insights of different systems and processes in physical chemistry. There have been several attempts to include Electron Correlation (EC) in the IQA approach, for example, through DFT and Hartree-Fock/Coupled-Cluster (HF/CC) transition densities. This work addresses the separation of EC in Fermi and Coulomb correlation and its effect upon the IQA analysis by taking into account spin-dependent one- and two-electron matrices $D^{\mathrm{HF/CC}}_{pσq σ}$ and $d^{\mathrm{HF/CC}}_{pσqσrτsτ}$ wherein $σ$ and $τ$ represent either of the $α$ and $β$ spin projections. We illustrate this approach by considering BeH$_2$,BH, CN$^-$, HF, LiF, NO$^+$, LiH, H$_2$O$\cdots$H$_2$O and C$_2$H$_2$, which comprise non-polar covalent, polar covalent, ionic and hydrogen bonded systems. The same and different spin contributions to ($i$) the net, interaction and exchange-correlation IQA energy components and ($ii$) delocalisation indices defined in the quantum theory of atoms in molecules are carefully examined and discussed. Overall, we expect that this kind of analysis will yield important insights about Fermi and Coulomb correlation in covalent bonding, intermolecular interactions and electron delocalisation in physical chemistry.
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