SPECTROSCOPIC EVIDENCE FOR BINARY OXYGEN CLUSTERS IN THE GAS PHASE.

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1967

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Ohio State University

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The 0-0 band of the $^{1}\Delta_{6}-^{3}\Sigma^{-}_{3}$ system of molecular oxygen has been examined at low temperatures using a White cell with an effective path of 30 meters. The integrated absorption coefficient at $87^{\circ}K$ is nearly twice as large as at room temperature. This intensity anomaly may be interpreted in terms of a ``clustering'' process, which includes both bound -pairs and collision pairs, both of which are expected to increase in importance at low temperatures. From the temperature dependence of the integrated absorption coefficient, a clustering energy $\Delta E=-360$ cal./mole is found. At present it is not possible to separate the effects of bound-pairs and collision pairs, since both of these contribute to the maximum of the pair-distribution function which governs the spectroscopic intensity. A direct confirmation of bound oxygen dimers will depend on observation of fine structure corresponding to the bound-states of the intermolecular potential.

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Author Institution: Department of Chemistry, Indiana University

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