The protonated water dimer: Extensive theoretical studies of H5O+2

Abstract

Ab initio quantum mechanical methods have been applied to the H5O+2 system, for which experiments are beginning to appear. These methods include basis sets up to triple-ζ plus double polarization plus f functions (TZ2Pf ) and levels of correlation up to coupled cluster including single, double, and perturbatively treated connected triple excitations [CCSD(T)]. The potential energy hypersurface is very flat and is sensitive to the level of theory. At the highest level of theory the global minimum is the structure with C2 symmetry, but the transition state with Cs symmetry is only 0.4 kcal/mol higher in energy. Some low energy excursions into C1 symmetry are carefully examined. The theoretical dissociation energy for the H3O+–H2O system is predicted to be 33.4 kcal/mol, and is in good agreement with experimental measurements. The harmonic vibrational frequencies and their infrared intensities at several levels of theory are also reported, and compared to the recent spectroscopic observations in Lee’s laboratory.