Revisit the landscape of protonated water clusters H+(H2O)n with <i>n</i> = 10–17: An <i>ab initio</i> global search

Abstract

Using a genetic algorithm incorporated with density functional theory, we explore the ground state structures of protonated water clusters H⁺(H₂O)_n with n = 10-17. Then we re-optimize the isomers at B97-D/aug-cc-pVDZ level of theory. The extra proton connects with a H₂O molecule to form a H₃O⁺ ion in all H⁺(H₂O)_10-17 clusters. The lowest-energy structures adopt a monocage form at n = 10-16 and core-shell structure at n = 17 based on the MP2/aug-cc-pVTZ//B97-D/aug-cc-pVDZ+ZPE single-point-energy calculation. Using second-order vibrational perturbation theory, we further calculate the infrared spectra with anharmonic correction for the ground state structures of H⁺(H₂O)_10-17 clusters at the PBE0/aug-cc-pVDZ level. The anharmonic correction to the spectra is crucial since it reproduces the experimental results quite well. The extra proton weakens the O-H bond strength in the H₃O⁺ ion since the Wiberg bond order of the O-H bond in the H₃O⁺ ion is smaller than that in H₂O molecules, which causes a red shift of the O-H stretching mode in the H₃O⁺ ion.