Fugel Malte, Beckmann Jens, Jayatilaka Dylan, Gibbs Gerald V, Grabowsky Simon
University of Bremen, Department 2: Biology/Chemistry, Institute of Inorganic Chemistry and Crystallography, Leobener Str. 3 and 7, Bremen, Germany.
University of Western Australia, School of Molecular Sciences, 35 Stirling Highway, Perth, WA, 6009, Australia.
Chemistry. 2018 Apr 20;24(23):6248-6261. doi: 10.1002/chem.201800453. Epub 2018 Apr 6.
There is a great variety of bond analysis tools that aim to extract information on the bonding situation from the molecular wavefunction. Because none of these can fully describe bonding in all of its complexity, it is necessary to regard a balanced selection of complementary analysis methods to obtain a reliable chemical conclusion. This is, however, not a feasible approach in most studies because it is a time-consuming procedure. Therefore, we provide the first comprehensive comparison of modern bonding analysis methods to reveal their informative value. The element-oxygen bond of neutral H XOH model compounds (X=Li, Be, B, C, N, O, F, Na, Mg, Al, Si, P, S, Cl) is investigated with a selection of different bond analysis tools, which may be assigned into three different categories: i) real space bonding indicators (quantum theory of atoms in molecules (QTAIM), the electron localizability indicator (ELI-D), and the Raub-Jansen index), ii) orbital-based descriptors (natural bond orbitals (NBO), natural resonance theory (NRT), and valence bond (VB) calculations), and iii) energy analysis methods (energy decomposition analysis (EDA) and the Q-analysis). Besides gaining a deep insight into the nature of the element-oxygen bond across the periodic table, this systematic investigation allows us to get an impression on how well these tools complement each other. Ionic, highly polarized, polarized covalent, and charge-shift bonds are discerned from each other.
有各种各样的键分析工具，旨在从分子波函数中提取有关键合情况的信息。由于这些工具都无法完全描述键合的所有复杂性，因此有必要综合选择互补的分析方法以获得可靠的化学结论。然而，在大多数研究中，这不是一种可行的方法，因为这是一个耗时的过程。因此，我们首次对现代键合分析方法进行了全面比较，以揭示它们的信息价值。我们使用一系列不同的键分析工具研究了中性H XOH模型化合物（X = Li、Be、B、C、N、O、F、Na、Mg、Al、Si、P、S、Cl）的元素-氧键，这些工具可分为三类：i）实空间键合指标（分子中的原子量子理论（QTAIM）、电子定域性指标（ELI-D）和劳布-扬森指数），ii）基于轨道的描述符（自然键轨道（NBO）、自然共振理论（NRT）和价键（VB）计算），以及iii）能量分析方法（能量分解分析（EDA）和Q分析）。除了深入了解整个周期表中元素-氧键的本质外，这项系统研究还让我们了解了这些工具之间的互补程度。离子键、高度极化键、极化共价键和电荷转移键能够相互区分。
