Details

Autor(en) / Beteiligte

• Liu, Fang
• Du, Likai

Titel

Decoding dominant interaction patterns in halogenated dimers: A journey from halogen bonding to Van der Waals interactions

Ist Teil von

• Computational and theoretical chemistry, 2024-03, Vol.1233, Article 114513

Ort / Verlag

Elsevier B.V

Erscheinungsjahr

2024

Link zum Volltext

Quelle

Elsevier ScienceDirect Journals Complete

Beschreibungen/Notizen

• This graphic abstract illustrates the diverse and collective non-covalent interactions in halogenated dimers, categorized into halogen bonds, hydrogen bonds and van der Waals complexes. It highlights the influence of substituent groups on interaction distance and pattern recognition. This study offers a clear visualization of molecular interactions essential for chemical and technological advancements. [Display omitted] •This study presents a groundbreaking analysis of non-covalent interactions within homodimeric complexes of fifteen halogenated molecules.•Employing a sophisticated combination of sampling, optimization protocols, and clustering algorithms, the research meticulously identifies and categorizes dominant interaction patterns from an extensive set of 30,000 optimized molecular structures.•A significant focus is on the intriguing roles of halogen bonds, ranging from halogen bonding to van der Waals interactions, in these complexes.•The research reveals how the closest contact distances within these complexes are significantly influenced by their substituent groups, shedding light on the nuanced interplay between various non-covalent interactions.•Additionally, the study innovatively uses dimensionality reduction techniques to visualize these interaction patterns, offering a crystal-clear depiction of the complex molecular interactions at play.•Importantly, the study also assesses the scalar relativistic effects on these distances, confirming minimal deviation from non-relativistic geometries.•This comprehensive exploration not only enhances our understanding of the molecular dynamics in halogenated dimers but also opens new avenues for their application in scientific and technological fields. Halogen bonds play a pivotal role in molecular recognition and self-assembly processes. In this work, we aim to provide a balanced understanding of diverse non-covalent interactions, from halogen bonding to van der Waals interactions in homodimeric complexes of fifteen halogenated molecules, represented as R-X (R = H, F, CH3, CF3, CH2CH; X = Cl, Br, I). Here, a meticulously designed sampling and optimization protocol is applied to generate a diverse set of molecular configurations and subsequently optimize them to identify dominant interaction patterns. The clustering algorithm revealed distinct interaction patterns that emerge from the 30,000 optimized structures. The proportion of each cluster and the energy stability are also reported. Dimensionality reduction techniques are employed to visualize these interaction modes, providing a clear representation of the underlying patterns. Notably, the distribution shape of the closest contact distance within these complexes is profoundly influenced by their substituent group. The interplay between halogen bonds and other non-covalent interactions is clearly identified. The scalar relativistic effects were evaluated for the closest contact distances with the ANOVA test. They did not show significant bias from their non-relativistic geometries. We hope these findings offer a holistic view of the intricate inter-molecular landscapes of halogenated dimers, paving the way for their informed utilization in various scientific and technological applications.