On the stability of clusters containing all-cis 1,2,3,4,5,6-hexafluorocyclohexane

Abstract

A computational study of strongly-bound triad clusters involving the all-cis 1,2,3,4,5,6-hexafluorocyclohexane molecule (F6C6H6) sandwiched between oppositely-charged ions, as well as the constituent ion/F6C6H6 dyad subunits, was undertaken at the B3LYP/6-31++G(d,p) level of theory. The model M+…F6C6H6…X− clusters involve the simultaneous attachment of a cation (M+) to the “negative” face of F6C6H6 (via interaction with the axial FC bonds) and an anion (X−) to the “positive” face of F6C6H6 (via the adjacent axial CH bonds).The stability of these moieties was investigated and it was found that the electrostatic interaction between M+ and X− is the dominant attractive contribution to the binding. The M+…F6C6H6…X− clusters were found to be more energetically stable than the most likely lowest-energy fragmentation products MX+F6C6H6. The FLi…F6C6H6…FLi cluster was also studied for the sake of comparison with the M+…F6C6H6…X− analogue.