Structure and Properties of Polyfluoride Fn(-) Clusters (n = 3-29)

Area of Science:

• Computational chemistry
• Quantum chemistry
• Materials science

Background:

• Polyfluorides (Fn) and their anions (Fn-) are of interest due to their unique electronic properties.
• Understanding their stability and structure is crucial for potential applications.

Purpose of the Study:

• To investigate the electronic and geometrical structures of neutral Fn and anionic Fn- polyfluorides.
• To determine the stability and superhalogen characteristics of these species.

Main Methods:

• Density Functional Theory (DFT) with generalized gradient approximation.
• Hybrid Hartree-Fock-DFT (HF-DFT) calculations.
• HF-DFT with long-range corrections were employed for theoretical analysis.

Main Results:

• For n > 4, Fn- anions exhibit multiple low-energy geometric states with a preference for higher symmetry.
• F29- displays Oh symmetry, and all Fn- (n≥3) are identified as superhalogen anions.
• Electron affinities, energies of formation, and binding energies show oscillatory behavior with increasing n.

Conclusions:

• Neutral Fn species are weakly bound by polarization forces.
• Fn- anions are relatively stable, particularly against the loss of F, F-, and F2-, but not F2.
• The study reveals distinct structural patterns for even-n and odd-n Fn- branches.