Water trimer cation

Abstract

By using density functional theory (DFT) and high-level ab initio theory, we have investigated the structure, interaction energy, electronic property, and IR spectra of the water trimer cation [(H2O) 3 + ]. Two structures of the water trimer cation [the H3O+ containing linear (3Lp) structure versus the ring (3OO) structure] are compared. For the complete basis set (CBS) limit of coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)], the 3Lp structure is 11.9 kcal/mol more stable than the 3OO structure. This indicates that the ionization of water clusters produce the hydronium cation moiety (H3O+) and the hydroxyl radical. It is interesting to note that the calculation results of the water trimer cation vary seriously depending on the calculation level. At the level of Moller–Plesset second-order perturbation (MP2) theory, the stability of 3OO is underestimated due to the underestimated O…O hemibonding energy. This stability is also underestimated even for the CCSD(T) single point calculations on the MP2-optimized geometry. For the 3OO structure, the MP2 and CCSD(T) calculations give closed-ring structures with a hemi-bond between two O atoms, while the DFT calculations show open-ring structures due to the overestimated O…O hemibonding energy. Thus, in order to obtain reliable stabilities and frequencies of the water trimer cation, the CCSD(T) geometry optimizations and frequency calculations are necessary. In this regard, the DFT functionals need to be improved to take into account the proper O…O hemibonding energy.