Aniban Xaiza, Ferrer Maxime, Montero-Campillo M Merced, Mata Ricardo A, Contreras-García Julia, Gimferrer Martí
Institut für Physikalische Chemie, Tammannstrasse 6, Göttingen 37077, Germany.
Instituto de Química Médica (CSIC), Juan de la Cierva 3, Madrid 28006, Spain.
Phys Chem Chem Phys. 2025 Jun 18;27(24):13033-13042. doi: 10.1039/d5cp01057h.
In this study, we introduce novel orbital decomposition approaches for analyzing non-covalent interactions (NCIs) and dispersion interaction densities (DID), termed o-NCI and o-DID, respectively. Orbital pair analyses offers an opportunity to analyse in-depth NCIs in four model dimer systems to which dispersion forces contribute to different extents: argon, methane, water and benzene-acetylene dimers. The comparative calculations reveal that intuitive interpretations based solely on nearby σ- and π-orbital interactions may overlook substantial contributions from more distant orbitals. For instance, in the benzene-acetylene dimer, interactions between π-orbitals significantly contribute to the overall dispersion energy, rivaling traditional σ bond contributions. Overall, this work establishes a comprehensive framework for understanding NCIs through the lens of orbital contributions and highlights that our interpretations must account for the intricate interplay between different interaction types. It also underlines the differences between NCI and local correlation energy decomposition, paving the way for advancements in the design and analysis of molecular systems based on NCIs.
在本研究中，我们引入了用于分析非共价相互作用（NCI）和色散相互作用密度（DID）的新型轨道分解方法，分别称为o-NCI和o-DID。轨道对分析为深入研究四种模型二聚体系统中的非共价相互作用提供了契机，在这些系统中色散力的贡献程度各不相同：氩、甲烷、水和苯 - 乙炔二聚体。对比计算表明，仅基于附近σ轨道和π轨道相互作用的直观解释可能会忽略更远距离轨道的重大贡献。例如，在苯 - 乙炔二聚体中，π轨道之间的相互作用对整体色散能有显著贡献，可与传统σ键的贡献相媲美。总体而言，这项工作通过轨道贡献的视角建立了一个理解非共价相互作用的综合框架，并强调我们的解释必须考虑不同相互作用类型之间的复杂相互作用。它还强调了非共价相互作用与局部相关能分解之间的差异，为基于非共价相互作用的分子系统设计和分析的进展铺平了道路。
