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| The nonbonded halogen halogen (X…X) interactions play an important role in crystal engineering and material sciences. The X…X bond involving two or more halogen centers results in a very interesting donor-acceptor interaction due to their complicated anistropic character, in which each halogen atom could simultaneously be a donor and an acceptor. Their potential energy surface (PES) shows a dual well potential feature. Here, we present a systematic theoretical investigation of the nature of the X…X interactions. The stable geometries, as well as the PES of X…X dimers (FX, X=Cl, Br, I) were extensively studied with a series of theoretical methods. Interestingly, we find that the hybrid wavefunction based approaches (such as MP2.5) are indeed a good choice to obtain improved binding energies (<0.05 kcal/mol error) with reduced computational cost. Among the DFT methods, the statistical errors are significantly dependent on the selected functionals. We anticipate this study could provide us some insights on the future understanding of the feature of X…X interactions in molecular packing. |
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| Keywords:Physical Chemistry; Halogen bond; Potential energy surface; Density Functional Theory |
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