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Anisotropies in electronic densities and electrostatic potentials of Halonium Ions: focus on Chlorine, Bromine and Iodine

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Abstract

Context

Why are the halonium cations so effective in forming strongly-bound complexes? We directed our research to address this question and we present electrostatic potential data for the valence-state halogen atoms X and halonium cations X+, where X = Cl, Br, I. The electron densities and electrostatic potentials of the halonium cations show considerably greater anisotropy than do the valence state halogens. The distances from the electrostatic potential surface maxima to the halogen nuclei are about 0.5 Å smaller than the distances from the electrostatic potential surface minima to the nuclei, giving the halonium cations each a more disk-like shape than the corresponding neutral valence state halogens. Their surface electrostatic potentials are totally consistent with the directionalities of halonium cations in complexes and the strengths of their interactions. To add perspective to this brief report, we have included calculations of the isotropic cation K+ and noble gas Kr.

Methods

The calculations of the electrostatic potentials of the valence states of the halogen atoms Cl, Br and I and the halonium cations Cl+, Br+ and I+, as well as K+ and Kr, on 0.001 au contours of their electronic densities were carried out with Gaussian O9 and the Wave Function Analysis – Surface Analysis Suite (WFA-SAS) at the M06-2X/6–31 + G(d,p) and M06-2X/3-21G* levels.

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Data availability

The datasets from the current study are available from the corresponding author on reasonable request.

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Acknowledgements

JSM gives many thanks and gratitude for the years of dedication given by Peter Politzer to the field of theoretical and computational chemistry, and for his continuing inspiration in my life. PR would like to dedicate this paper to Peter Politzer and he will always be remembered as a great scientist and a great human being.

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The authors declare that no funds, grants, or other support were received during the preparation of this manuscript.

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Authors and Affiliations

  1. Computational Chemistry Group, Department of Chemistry, Faculty of Science, University of Mauritius, Réduit, 80837, Mauritius

    Ponnadurai Ramasami

  2. Centre of Natural Product Research, Department of Chemical Sciences, University of Johannesburg, Doornfontein Campus, Johannesburg, 2028, South Africa

    Ponnadurai Ramasami

  3. Department of Chemistry, University of New Orleans, New Orleans, LA, 70148, USA

    Jane S. Murray

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  1. Ponnadurai Ramasami
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  2. Jane S. Murray
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Contributions

Both authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by Ponnadurai Ramasami and Jane S. Murray. The first draft of the manuscript was written by Jane S. Murray. Both authors read and approved the final manuscript.

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Correspondence to Jane S. Murray.

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Ramasami, P., Murray, J.S. Anisotropies in electronic densities and electrostatic potentials of Halonium Ions: focus on Chlorine, Bromine and Iodine. J Mol Model 30, 81 (2024). https://doi.org/10.1007/s00894-024-05869-5

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