What is the exchange-repulsion energy? Insight by partitioning into physically meaningful contributions.

IF 2.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Chemphyschem Pub Date : 2024-11-21 DOI:10.1002/cphc.202400887

Johannes Henrichsmeyer, Michael Thelen, Reinhold F Fink

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Abstract

It is shown that the exchange repulsion energy, Exr, can be rationalized by partitioning the respective energy expression for two systems with Hartree-Fock orbitals into physically meaningful contributions. A division of Exr into a positive kinetic and a negative potential part is possible, but these contributions correlate only poorly with the actual exchange repulsion energy. A more meaningful partitioning is derived, where all kinetic energy contributions are collected in a term that vanishes for exact Hartree-Fock orbitals due to their stationarity conditions. The remaining terms can be distinguished into an exchange integral contribution as well as contributions to the repulsion energy with two, three and four orbital indices. The forms, relationships and absolute sizes of these terms suggest an intuitive partitioning of the exchange repulsion energy into Molecular Orbital Pair Contributions to the Exchange repulsion energy (MOPCE). Insight into the analytic form and quantitative size of these contributions is provided by considering the 3Σ+u (1σg1σu) state of the H2 molecule, the water dimer, as well as an argon atom interacting with Cl2 and N2.

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什么是交换-反推能量？通过将其划分为有物理意义的贡献来了解。

研究表明，可以通过将两个具有哈特里-福克（Hartree-Fock）轨道的系统各自的能量表达式划分为有物理意义的贡献来合理解释交换斥能 Exr。将 Exr 划分为正动能部分和负势能部分是可行的，但这些贡献与实际交换斥能的相关性很差。我们得出了一种更有意义的划分方法，即把所有动能贡献都收集到一个项中，由于精确哈特里-福克轨道的静止条件，这个项消失了。剩下的项可以区分为交换积分贡献以及两个、三个和四个轨道指数对斥力能的贡献。这些项的形式、关系和绝对大小表明，可以将交换斥能直观地划分为分子轨道对交换斥能贡献（MOPCE）。通过考虑 H2 分子的 3Σ+u (1σg1σu) 状态、水二聚体以及与 Cl2 和 N2 相互作用的氩原子，我们可以深入了解这些贡献的解析形式和定量大小。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Chemphyschem 化学-物理：原子、分子和化学物理

CiteScore

4.60

自引率

3.40%

发文量

425

审稿时长

1.1 months

期刊介绍： ChemPhysChem is one of the leading chemistry/physics interdisciplinary journals (ISI Impact Factor 2018: 3.077) for physical chemistry and chemical physics. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. ChemPhysChem is an international source for important primary and critical secondary information across the whole field of physical chemistry and chemical physics. It integrates this wide and flourishing field ranging from Solid State and Soft-Matter Research, Electro- and Photochemistry, Femtochemistry and Nanotechnology, Complex Systems, Single-Molecule Research, Clusters and Colloids, Catalysis and Surface Science, Biophysics and Physical Biochemistry, Atmospheric and Environmental Chemistry, and many more topics. ChemPhysChem is peer-reviewed.