Poater Jordi, Andrada Diego M, Solà Miquel, Foroutan-Nejad Cina
Departament de Química Inorgànica i Orgànica and IQTCUB, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Catalonia, Spain.
ICREA, Pg. Lluís Companys 23, 08010 Barcelona, Spain.
Phys Chem Chem Phys. 2022 Jan 26;24(4):2344-2348. doi: 10.1039/d1cp04135e.
Here, we provide evidence of the path-dependency of the energy components of the energy decomposition analysis scheme, EDA, by studying a set of thirty-one closed-shell model systems with the symmetry point group. For each system, we computed EDA components from nine different pathways and numerically showed that the relative magnitudes of the components differ substantially from one path to the other. Not surprisingly, yet unfortunately, the most significant variations in the relative magnitudes of the EDA components appear in the case of species with bonds within the grey zone of covalency and ionicity. We further discussed that the role of anions and their effect on arbitrary Pauli repulsion energy components affects the nature of bonding defined by EDA. The outcome variation by the selected partitioning scheme of EDA might bring arbitrariness when a careful comparison is overlooked.
在此，我们通过研究一组具有 对称点群的 31 个闭壳层模型系统，提供了能量分解分析方案（EDA）能量成分路径依赖性的证据。对于每个系统，我们从九条不同路径计算了 EDA 成分，并通过数值表明，各成分的相对大小在不同路径之间存在显著差异。不出所料但不幸的是，EDA 成分相对大小的最显著变化出现在共价性和离子性处于灰色区域的键的物种情况中。我们进一步讨论了阴离子的作用及其对任意泡利排斥能成分的影响，这会影响由 EDA 定义的键合性质。当忽略仔细比较时，EDA 所选划分方案导致的结果变化可能会带来随意性。
