Bonding in Ion Clusters. I. O4+

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Abstract
The O2–O2 +bond energy has been determined to be 0.42 eV from the temperature variation of the equilibrium constant for the reaction: O2+O2 +=O4 +. The rotational entropy of the O4 + by the ``loose'' cluster model, in which 6 rotational degrees of freedom are assumed, appears to be too large for the observed entropy change, ΔS 293°= —20.6 e.u. Approximately half of the bond energy can be ascribed to a simple ion‐induced dipole interaction if account is taken of the variation in field strength over the O2 molecule by use of a very simple model. The explanation for the residual bond energy discrepancy might be that the polarizability of O2 is larger than the low‐field experimental value at high field strengths such as those ∼3 Å from an ion. The experimental method described is of wide applicability in determining bond energies in ion clusters.

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