Martín Pendás Ángel, Francisco Evelio
Departamento de Química Física y Analítica, Universidad de Oviedo, 33006, Oviedo, Spain.
Nat Commun. 2022 Jun 9;13(1):3327. doi: 10.1038/s41467-022-31036-6.
Chemical bonding theory is of utmost importance to chemistry, and a standard paradigm in which quantum mechanical interference drives the kinetic energy lowering of two approaching fragments has emerged. Here we report that both internal and external reference biases remain in this model, leaving plenty of unexplored territory. We show how the former biases affect the notion of wavefunction interference, which is purportedly recognized as the most basic bonding mechanism. The latter influence how bonding models are chosen. We demonstrate that the use of real space analyses are as reference-less as possible, advocating for their use. Delocalisation emerges as the reference-less equivalent to interference and the ultimate root of bonding. Atoms (or fragments) in molecules should be understood as a statistical mixture of components differing in electron number, spin, etc.
化学键理论对化学至关重要，一种量子力学干涉驱动两个接近的片段动能降低的标准范式已经出现。在此我们报告，该模型中仍然存在内部和外部参考偏差，留下了大量未探索的领域。我们展示了前者的偏差如何影响波函数干涉的概念，而波函数干涉据称被认为是最基本的键合机制。后者影响键合模型的选择。我们证明，使用实空间分析尽可能无参考，提倡使用它们。离域作为无参考的等同于干涉的概念以及键合的最终根源出现。分子中的原子（或片段）应被理解为在电子数、自旋等方面不同的组分的统计混合。
