Computational investigation of LiF containing hypersalts

Abstract

This study explores the design of possible hypersalts starting from the hyperhalogen Li₃F₄ plus a Li atom and the hyperalkali Li₄F₃ plus a F atom. The investigation uses a multistep composite computational job that follows the same setup of the CBS-QB3 method, and uses B3LYP in combination with the CBSB7 + basis set for geometry optimizations. Adiabatic ionization energies (AIE), adiabatic electron affinities (AEA), HOMO–LUMO energy gaps, and NBO's are calculated for each presented species. Results confirm that the newly constructed hyperalkalis Li₄F₃, which has two isomers A and B, result in even lower AIE (3.83 eV and 3.65 eV for hyperalkali A and B, respectively) than the starting superalkali Li₂F. The study also confirms the structures for the designed hyperhalogens Li₃F₄ (two isomers A and B) with higher AEA (7.70 eV and 5.63 eV for hyperhalogen A and B, respectively) than the superhalogen LiF₂ building block. Hyperhalogens A and B in combination with a Li atom and hyperalkali A and B in combination with a F atom are used to create hypersalts. This yields three possible hypersalts A, B(C), and D with the formula Li₄F₄. Hypersalt A has the larger binding energy for dissociation into neutral fragments equal to 7.82 eV. Hypersalt C has the lower binding energy for dissociation into neutrals of 7.17 eV and hypersalt D the larger binding energy for dissociation into ions.