DFT-steric-based energy decomposition analysis of intermolecular interactions
DFT-steric-based energy decomposition analysis of intermolecular interactions
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DOI：
10.1007/s00214-014-1484-7
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发表时间：
2014-04-08
影响因子：
1.7
通讯作者：
Cisneros, G. Andres
中科院分区：
文献类型：
--
作者：
Fang, Dong;Piquemal, Jean-Philip;Cisneros, G. Andres
提出了一种新的基于密度泛函理论(DFT)空间分析的能量分解分析(EDA)方法。与约束空间轨道变分(CSOV)和分子中原子的Bader量子理论(QTAIM)的拓扑分析结果进行了比较。这两种分析从不同的角度解释了二聚体形成的驱动力。密度泛函空间分析的组份与氢键二聚体的总相互作用能有很好的线性关系。观察到新的EDA方法中的某些成分，如空间能，有利于二聚体的形成。此外，通过比较CSOV和DFT立体分析之间的不同贡献，可以更深入地了解各自组成部分的物理意义。在QTAIM分析中发现，除了总相互作用能外，DFT空间能还与不同分子体系在不同模式下临界点的电子密度有关，这定性地解释了立体能与总相互作用能之间的线性关系。DFT空间能被发现代表了二聚体形成时电子密度的空间排列所产生的影响，这让人想起化学体系中的空间效应。
Application of a novel energy decomposition analysis (EDA) based on the recently introduced density functional theory (DFT) steric analysis is presented. The method is compared with results from the constrained space orbital variations (CSOV) and Bader's quantum theory of atoms in molecules (QTAIM) topological analysis. These two analyses explain the driving forces for the formation of dimers from different perspectives. The components of the DFT steric analysis are shown to have good linear relationships with the total interaction energy for hydrogen-bonding dimers. It is observed that some components from the new EDA method, such as steric energy, favor the formation of dimers. Moreover, comparison of the different contributions between CSOV and the DFT steric analysis provides additional insights into the physical meaning of the respective components. In addition to the total interaction energy, DFT steric energy has been found to correlate with the electron density at critical points from QTAIM analysis in different patterns for different molecular systems, which qualitatively accounts for the linear relationships between the steric and total interaction energy. The DFT steric energy is found to represent effects arising from the spatial arrangement of the electron density when dimers form, reminiscent of the steric effects invoked in chemical systems.