Stöhr Martin, Sadhukhan Mainak, Al-Hamdani Yasmine S, Hermann Jan, Tkatchenko Alexandre
Department of Physics and Materials Science, University of Luxembourg, Luxembourg, L-1511, Luxembourg.
Department of Chemistry, Indian Institute of Technology Kanpur, Kalyanpur, Kanpur, 208 016, India.
Nat Commun. 2021 Jan 8;12(1):137. doi: 10.1038/s41467-020-20473-w.
Mutual Coulomb interactions between electrons lead to a plethora of interesting physical and chemical effects, especially if those interactions involve many fluctuating electrons over large spatial scales. Here, we identify and study in detail the Coulomb interaction between dipolar quantum fluctuations in the context of van der Waals complexes and materials. Up to now, the interaction arising from the modification of the electron density due to quantum van der Waals interactions was considered to be vanishingly small. We demonstrate that in supramolecular systems and for molecules embedded in nanostructures, such contributions can amount to up to 6 kJ/mol and can even lead to qualitative changes in the long-range van der Waals interaction. Taking into account these broad implications, we advocate for the systematic assessment of so-called Dipole-Correlated Coulomb Singles in large molecular systems and discuss their relevance for explaining several recent puzzling experimental observations of collective behavior in nanostructured materials.
电子之间的相互库仑相互作用会引发大量有趣的物理和化学效应，尤其是当这些相互作用涉及在大空间尺度上的许多波动电子时。在此，我们详细识别并研究范德华复合物和材料背景下偶极量子涨落之间的库仑相互作用。到目前为止，由于量子范德华相互作用导致的电子密度变化所产生的相互作用被认为极其微小。我们证明，在超分子系统以及嵌入纳米结构的分子中，这种贡献可达6 kJ/mol，甚至会导致长程范德华相互作用的定性变化。考虑到这些广泛影响，我们主张对大分子系统中所谓的偶极相关库仑单重态进行系统评估，并讨论它们对于解释纳米结构材料中近期一些关于集体行为的令人困惑的实验观测结果的相关性。
