The structures of cyclic dihydronium cations.

Recent experimental discoveries have revealed the existence of hitherto unexpected cyclic hydronium di-cations trapped within crystal structures. The molecular formulas are (H(14)O(6))(2+), present as two isomers, four- and six-member cyclic structures, and (H(18)O(8))(2+), an eight-member cyclic structure. As these unprecedented hydronium species are stabilized by the crystal structures in which they are captured, the question arises whether they could be stable as independent species as, for example, in solution or gas phase. Quantum mechanical density functional theory calculations are used to investigate this question. We find these doubly charged cyclic hydronium structures to be energetically stable and, as between the four- and six-member structures, the former has more binding energy than the latter. We also determine the theoretically optimized structures for all three ions and give their calculated atomic charges for both their crystal and optimized geometries.