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Formation of Enormously Strongly Bound Anionic Clusters Predicted in Binary Superacids.

Marcin Czapla1, Olimpia Ciepła1, Jakub Brzeski1

  • 1Laboratory of Quantum Chemistry, Department of Theoretical Chemistry, Faculty of Chemistry , University of Gdańsk , Wita Stwosza 63 , 80-308 Gdańsk , Poland.

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PubMed
Summary

Superhalogen anionic clusters like (AlF4(HF)n)-, (AsF6(HF)n)-, and (SbF6(HF)n)- were predicted in superacid solutions. These strongly bound anions exhibit exceptionally high vertical electron detachment energies, exceeding 10 eV.

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Area of Science:

  • Computational chemistry
  • Materials science
  • Superacid chemistry

Background:

  • Superacids like HF/AlF3, HF/AsF5, and HF/SbF5 are potent Lewis-Brønsted acids.
  • Anionic clusters can exhibit unique electronic properties, including superhalogen characteristics.

Purpose of the Study:

  • To predict the formation and properties of anionic clusters in binary superacid solutions.
  • To investigate the superhalogen nature and electron binding energies of these clusters.

Main Methods:

  • Ab initio calculations were employed to model the electronic structure of anionic clusters.
  • Vertical electron detachment energies (VDEs) were calculated for various cluster sizes.

Main Results:

  • The formation of (AlF4(HF)n)-, (AsF6(HF)n)-, and (SbF6(HF)n)- anionic clusters was predicted.
  • All investigated systems showed extremely strong binding, with VDEs significantly exceeding 10 eV.
  • The largest VDEs were predicted for (AlF4(HF)12)-, (AsF6(HF)12)-, and (SbF6(HF)12)- anions (13.96-14.03 eV).

Conclusions:

  • The studied binary superacid solutions can form stable superhalogen anions.
  • These anions possess exceptionally high electron binding energies, setting new records in reported VDEs.