1. Anisotropies in electronic densities and electrostatic potentials of Halonium Ions: focus on Chlorine, Bromine and Iodine.
- Author
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Ramasami, Ponnadurai and Murray, Jane S.
- Subjects
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ELECTRIC potential , *CHLORINE , *BROMINE , *SURFACE potential , *IODINE , *ELECTRON density , *WAVE analysis , *IONS , *ELECTROSTATIC interaction - 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. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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