Microsolvation of H2O+, H3O+, and CH3OH2+ by He in a cryogenic ion trap: structure of solvation shells

Abstract

Due to the weak interactions of He atoms with neutral molecules and ions, the preparation of size-selected clusters for the spectroscopic characterization of their structures, energies, and large amplitude motions is a challenging task. Herein, we generate H₂O⁺He_n (n ≤ 9) and H₃O⁺He_n (n ≤ 5) clusters by stepwise addition of He atoms to mass-selected ions stored in a cryogenic 22-pole ion trap held at 5 K. The population of the clusters as a function of n provides insight into the structure of the first He solvation shell around these ions given by the anisotropy of the cation–He interaction potential. To rationalize the observed cluster size distributions, the structural, energetic, and vibrational properties of the clusters are characterized by ab initio calculations up to the CCSD(T)/aug-cc-pVTZ level. The cluster growth around both the open-shell H₂O⁺ and closed-shell H₃O⁺ ions begins by forming nearly linear and equivalent OH⋯He hydrogen bonds (H-bonds) leading to symmetric structures. The strength of these H-bonds decreases slightly with n due to noncooperative three-body induction forces and is weaker for H₃O⁺ than for H₂O⁺ due to both enhanced charge delocalization and reduced acidity of the OH protons. After filling all available H-bonded sites, addition of further He ligands around H₂O⁺ (n = 3–4) occurs at the electrophilic singly occupied 2p_z orbital of O leading to O⋯He p-bonds stabilized by induction and small charge transfer from H₂O⁺ to He. As this orbital is filled for H₃O⁺, He atoms occupy in the n = 4–6 clusters positions between the H-bonded He atoms, leading to a slightly distorted regular hexagon ring for n = 6. Comparison between H₃O⁺He_n and CH₃OH₂⁺He_n illustrates that CH₃ substitution substantially reduces the acidity of the OH protons, so that only clusters up to n = 2 can be observed. The structure of the solvation sub-shells is visible in both the binding energies and the predicted vibrational OH stretch and bend frequencies.