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Issue 43, 2016
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Characterization of N⋯O non-covalent interactions involving σ-holes: “electrostatics” or “dispersion”

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In this article, the existence of N⋯O noncovalent interactions was explored in per-halo substituted ammonia–water complexes. Optimized geometry at the MP2/aug-cc-pVTZ level shows that the N⋯O distance in all complexes is less than the sum of the vdW radii of N and O. The strength of these contacts was directly dependent on the extent of chlorine substitution on N or O atoms. Also, the level of theory and the basis set employed for the binding energy calculations have a direct effect on the strength of the N⋯O contacts. Energy decomposition analysis reveals that dispersion was the major contributor towards the stability of these contacts followed by electrostatic energy. The topological analysis further confirmed the existence of N⋯O contacts due to the presence of a bond critical point between the N and the O atom in all the complexes. These contacts have characteristics of a σ-hole interaction with the NBO analysis revealing that the primary charge transfer in all the complexes is occurring from O(lp) to σ*(N–X) orbitals, confirming these interactions to be predominantly in the category of pnicogen bonds.

Graphical abstract: Characterization of N⋯O non-covalent interactions involving σ-holes: “electrostatics” or “dispersion”

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The article was received on 25 Aug 2016, accepted on 29 Sep 2016 and first published on 29 Sep 2016

Article type: Paper
DOI: 10.1039/C6CP05899J
Citation: Phys. Chem. Chem. Phys., 2016,18, 29946-29954
  • Open access: Creative Commons BY-NC license
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    Characterization of N⋯O non-covalent interactions involving σ-holes: “electrostatics” or “dispersion”

    R. Shukla and D. Chopra, Phys. Chem. Chem. Phys., 2016, 18, 29946
    DOI: 10.1039/C6CP05899J

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