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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Quantum chemical investigation of attractive non-covalent interactions between halomethanes and rare gases
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Quantum chemical investigation of attractive non-covalent interactions between halomethanes and rare gases

机译：卤代甲烷与稀有气体之间有吸引力的非共价相互作用的量子化学研究

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The interaction between rare gas atoms and trifluoromethylhalides and iodomethane is investigated using ab initio and density functional theory (DFT) methods: MP2, CCSD, B3LYP, M06, M06-L, M06-2X, M06-HF, X3LYP, PBE, B97-D, B3LYP-D3, and M06-L-D3, in combination with the aug-cc-pVTZ and aug-cc-pVTZ-PP basis sets. A weakly attractive interaction is observed for all complexes, whose strength increases as the rare gas and halogen bond donor become more polarizable, and as the group bound to the halogen bond donor becomes more electron-withdrawing. The separation between iodine and krypton in the complex CF 3I?Kr, calculated at the MP2 and B3LYP-D3 levels of theory, agrees very well with recent experimental results (Stephens, S. L.; Walker, N. R.; Legon, A. C. J. Chem. Phys.2011, 135, 224309). Analysis of the ability of theoretical methods to account for the dispersion interaction present in these complexes leads to the conclusion that MP2 and B3LYP-D3, which produce very similar results, are the better performing methods, followed by B97-D and the M06 suite of functionals; the popular B3LYP as well as X3LYP perform poorly and significantly underestimate the interaction strength. The orbitals responsible for the interaction are identified through Edmiston-Ruedenberg localization; it is shown that, by combining the key orbitals, it is possible to observe a molecular orbital picture of a σ-hole interaction.
机译：使用从头算和密度泛函理论（DFT）方法研究了稀有气体原子与三氟甲基卤化物和碘甲烷之间的相互作用：MP2，CCSD，B3LYP，M06，M06-L，M06-2X，M06-HF，X3LYP，PBE，B97- D，B3LYP-D3和M06-L-D3，以及aug-cc-pVTZ和aug-cc-pVTZ-PP基集。对于所有配合物都观察到弱的吸引力相互作用，其相互作用随着稀有气体和卤素键供体的极化性增加以及与卤素键供体结合的基团的吸电子性增加而增强。在理论上以MP2和B3LYP-D3的水平计算出的复合CF 3I？Kr中碘和k的分离与最近的实验结果非常吻合（Stephens，SL; Walker，NR; Legon，ACJ Chem。Phys.2011 ，135，224309）。分析这些复合物中存在的色散相互作用的理论方法的能力得出的结论是，产生非常相似结果的MP2和B3LYP-D3是性能更好的方法，其次是B97-D和M06套件。功能;流行的B3LYP和X3LYP的效果都很差，并且大大低估了交互强度。通过Edmiston-Ruedenberg本地化确定了相互作用的轨道。结果表明，通过组合关键轨道，可以观察到σ-空穴相互作用的分子轨道图。

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