4.6 Article

Gas phase hydration of organic ions

Journal

PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 10, Issue 32, Pages 4827-4834

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/b809440n

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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 (Delta H-n-1,n(circle)) 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 Delta H-n-1,n(circle) 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 center dot+ 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.

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