UPMC Université Paris 06, UMR 7075, Laboratoire de Dynamique, Interactions et Réactivité (LADIR), F-75005, Paris, France.
J Phys Chem A. 2011 Jun 23;115(24):6688-701. doi: 10.1021/jp202867t. Epub 2011 May 23.
Spectroscopic properties of 1:n complexes (n = 1, 2, and 3) formed between an oxirane molecule and water clusters have been evaluated using experimental techniques (FTIR spectroscopy using a new supersonic jet experiment coupled to the infrared AILES beamline of synchrotron SOLEIL and also cryogenic neon matrix device) and theoretical approaches (SAPT, ab initio, DFT, and topological analyses). From a systematic comparison between the theoretical results (obtained with both wave function based methods and several newly hydrogen bonded adapted functionals) with the available experimental results on the studied compounds, it was concluded that only the wave function based methods (particularly coupled clusters ones) are able to well describe these compounds, while the newly hydrogen bonded adapted functionals (long-range and/or dispersion-corrected ones and also double hybrids) cannot adequately describe all the spectroscopic properties in a systematic way. The MP2 method, although more expensive than DFT, still offers a reliable method to study both isolated molecules and hydrogen bonded complexes provided the contribution of the dispersion energy in total energy is properly taken into account. The nature of interaction between oxirane and water molecules has been analyzed using the symmetry adapted perturbation theory (SAPT) method. It was evidenced that the water-oxirane interaction corresponds to the hydrogen-bonded systems with a large contribution of the dispersion energy. The nature of the oxirane-water bonding has been studied using two topological methods: atoms in molecules and electron-localization function (ELF). Geometrical structures of the titled complexes were rationalized from the spatial arrangement of ELF attractors. Secondary interaction was also accounted for the bond critical points found at H(oxirane)···O(water) bond paths.
环氧化物分子与水分子形成的 1:n 配合物（n = 1、2 和 3）的光谱性质已通过实验技术（使用新的超声射流实验与同步辐射 SOLEIL 的红外 AILES 光束线耦合的傅里叶变换红外光谱，以及低温 neon 基质设备）和理论方法（SAPT、从头算、DFT 和拓扑分析）进行了评估。通过对理论结果（使用基于波函数的方法和几种新的氢键适应函数获得）与研究化合物的可用实验结果进行系统比较，可以得出结论，只有基于波函数的方法（特别是耦合簇方法）才能很好地描述这些化合物，而新的氢键适应函数（远程和/或色散校正的函数以及双杂交方法）不能系统地很好地描述所有光谱性质。MP2 方法虽然比 DFT 更昂贵，但仍然提供了一种可靠的方法来研究孤立分子和氢键配合物，只要适当考虑了色散能在总能量中的贡献。使用对称适应微扰理论（SAPT）方法分析了环氧化物和水分子之间的相互作用性质。结果表明，水分子与环氧化物的相互作用对应于氢键体系，其中色散能的贡献很大。使用两种拓扑方法：分子中的原子和电子局域化函数（ELF）研究了环氧化物-水键的性质。从 ELF 吸引子的空间排列来合理化标题配合物的几何结构。在 H（环氧化物）···O（水）键路径上发现的键临界点处，还考虑了次级相互作用。
