The evolution of the monoelectron dihydrogen bond H⋯e⋯H in the symmetric and asymmetric cluster anions (FH)n{e}(HF)m

Abstract

Using the aug-cc-pVDZ basis set supplemented with diffuse bond functions (BF), the evolution of the monoelectron dihydrogen bond H⋯e⋯H in the symmetric (n=m=2–5) and asymmetric (n,m:3,1;3,2;4,2;4,3) cluster anions (FH)n{e}(HF)m have been studied. When n=m=3, 4, 5, and n, m: 3, 2 the H⋯e⋯H bond evolves into the FH–e–HF monoelectron bimolecular bond. While in some asymmetric cluster anions (n,m:4,2;4,3) the FH–e–HF bond changes to H–e–HF bond, and some bond rearrangements occur in the larger subunit (HF)4 at the same time. This evolution shows a size effect of the subunits on the structure and the bond for the molecular cluster anions.