The gas‐phase equilibria of solvation reactions of O+2 and O2 ions with O2 were measured with a pulsed electron‐beam high‐pressure mass spectrometer. van’t Hoff plots of the equilibrium constants lead to the determination of the thermochemical stabilities for O+2(O2)n with n=1–8 and for O2(O2)n with n=1–7. The fashion of the bonding in the clusters O+2(O2)n and O2(O2)n changes drastically from covalent to electrostatic one between n=2 and 3, and n=1 and 2, respectively. That is, the first shells formed for these positive and negative cluster ions are O+2(O2)2 and (O2‐‐‐O2). The formation of the second shells, O+2(O2)2(O2)2 and (O2‐‐‐O2)−(O2)2, are also observed, but they are only slightly more stable than larger clusters toward dissociation.

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