DOI: 10.1002/cphc.202000172

Metastable Dianions and Dications

A theoretical study of metastable dianions and dications has been carried out at the CCSD(T)//MP2 level. MX₃²⁻ and LX₄²⁻ (M=Li and Na, L=Be and Mg, X=F and Cl) have been considered as dianions, M₃X²⁺ (M=Li and Na, X=F and Cl), YH₃²⁺ and ZH₄²⁺ (Y=F and Cl and Z=O, S) as dications. Minima structures are found in all cases, but they are less stable than the corresponding dissociated pair of mono‐ions. The dissociation profile of the molecules in two mono‐ions has been explored showing in all cases a maximum that prevent their spontaneous dissociation. The strength and nature of the chemical bond in the dianions and dications have been analyzed with the QTAIM, NBO and LMOEDA method and compared to the corresponding monoanions and monocations.