Gas phase hydration of organic ions

Abstract

In this work, we study the hydration phenomenon on a molecular level in the gas phase where a selected number of water molecules can interact with the organic ion of interest. The stepwise binding energies (ΔH°_n−1,n) of 1–7 water molecules to the phenyl acetylene cation are determined by equilibrium measurements using an ion mobility drift cell. The stepwise hydration energies ΔH°_n−1,n are nearly constant at 39.7 ± 6.3 kJ mol⁻¹ from n = 1 to 7. The entropy change is larger in the n = 7 step, suggesting cyclic or cage-like water structures. No water addition is observed on the ionized phenyl acetylene trimer consistent with cyclization of the trimer ion to form triphenyl benzene cations C₂₄H₁₈˙⁺ which are expected to interact weakly with the water molecules due to steric interactions and the delocalization of the charge on the large organic ion. The work demonstrates that hydration studies of organic ions can provide structural information on the organic ions.