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The cooperativity between the σ-hole and π-hole interactions in the ClO···XONO2/XONO···NH3 (X = Cl, Br, I) complexes

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Abstract

The second-order Møller–lesset perturbation theory (MP2) calculations have been performed to investigate the cooperativity between the σ-hole and π-hole interactions in the ClO···XONO2/XONO···NH3 (X = Cl, Br, I) complexes. The σ-holes and π-holes have been found on the outer surfaces of XONO2/XONO: the σ-hole is outside the halogen atoms approximately along the extension of X–O bond, and the π-hole is above and below the nitrogen atom and the terminal oxygen atom. Both the σ-hole and π-hole interaction energies are consistent with the most positive electrostatic potentials (V S, max) of the σ-holes and π-holes, indicating that electrostatic interactions play an important role in the σ-hole and π-hole interactions. From a two- to a three-body interaction, the interaction energies, binding distances, and infrared vibrational frequencies prove that there is negative cooperativity between the σ-hole and π-hole interactions. In the formation of the σ-hole and π-hole interactions, the electric fields of the negative sites ClO and NH3 cause the decrease of the electronic density of the σ-hole and π-hole regions of XONO2. Due to the negative effect between the σ-hole and π-hole interactions, the decreased regions of electronic density of the σ-hole and π-hole are somewhat contracted.

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Acknowledgments

This project was supported by the National Natural Science Foundation of China (Contract Nos.: 21371045, 21373075, 21372062, 21102033, 21171047), and the Education Department Foundation of Hebei Province (Contract Nos.: ZH2012106, ZD20131053).

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Authors and Affiliations

  1. Institute of Computational Quantum Chemistry, College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang, 050024, People’s Republic of China

    Ting Lang, Xiaoyan Li, Lingpeng Meng, Shijun Zheng & Yanli Zeng

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  1. Ting Lang
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  2. Xiaoyan Li
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  3. Lingpeng Meng
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  4. Shijun Zheng
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  5. Yanli Zeng
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Correspondence to Yanli Zeng.

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Lang, T., Li, X., Meng, L. et al. The cooperativity between the σ-hole and π-hole interactions in the ClO···XONO2/XONO···NH3 (X = Cl, Br, I) complexes. Struct Chem 26, 213–221 (2015). https://doi.org/10.1007/s11224-014-0486-3

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  • DOI: https://doi.org/10.1007/s11224-014-0486-3

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