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Planar tetracoordinate fluorine atom: global minimum with viable possibility.

Kangkan Sarmah1, Amlan J Kalita1, Ankur Kanti Guha1

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Researchers discovered a true planar tetracoordinate fluorine (ptF) atom, a rare structure, as the global minimum in a new H3Li4F- cluster. This finding challenges previous predictions and opens new avenues in hypercoordinate chemistry.

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Area of Science:

  • Computational Chemistry
  • Materials Science
  • Inorganic Chemistry

Background:

  • Planar hypercoordinate structures are increasingly observed, particularly with second-row elements.
  • Previous predictions of planar tetracoordinate fluorine (ptF) in group 13 clusters were invalidated by high-level calculations, deeming them unstable.
  • A genuine, stable ptF structure has remained elusive in scientific literature.

Purpose of the Study:

  • To propose and computationally verify the existence of an unprecedented planar tetracoordinate fluorine (ptF) structure.
  • To investigate the stability and electronic properties of the proposed ptF within a novel cluster.
  • To explore the potential for similar structures with heavier alkali metals.

Main Methods:

  • Utilized density functional theory (DFT) and ab initio calculations to determine the global minimum energy structure.
  • Performed bonding analysis to understand the stabilization mechanisms of the ptF.
  • Conducted natural charge analysis to elucidate charge distribution and electrostatic interactions.

Main Results:

  • Identified a stable planar tetracoordinate fluorine (ptF) as the global minimum in the C2V symmetric H3Li4F- cluster.
  • Confirmed similar stable ptF structures with heavier alkali metals (Na, K).
  • Demonstrated that multicentre bonding and significant electrostatic attraction between the negatively charged fluorine and positively charged lithium centers stabilize the ptF structure.

Conclusions:

  • The study presents the first computationally verified, stable planar tetracoordinate fluorine (ptF) structure.
  • The findings indicate that electrostatic interactions, not aromaticity, are key to stabilizing this unique structure.
  • The dynamically stable cluster is predicted to be experimentally detectable in the gas phase.