Collision-Induced Absorption Spectrum of Gaseous Oxygen at Low Temperatures and Pressures. II. The Simultaneous Transitions Δg1 + 1Δg ← 3Σg− + 3Σg− and Δg1 + 1Σg+ ← 3Σg− + 3Σg−
- 15 December 1969
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 51 (12) , 5284-5289
- https://doi.org/10.1063/1.1671946
Abstract
The collision-induced absorption spectra have been measured at room temperature and at 87°K for bands in the Δg1 + 1Δg ← 3Σg− + 3Σg− and Δg1 + 1Σg+ ← 3Σg− + 3Σg− simultaneous electronic systems for oxygen. The binary absorption coefficients were found to increase with decreasing temperature for Δg1 + 1Δg ← 3Σg− + 3Σg−. The band shapes for this system suggest that the Hamiltonian which is responsible for intensity borrowing depends on the angular orientation of the O2 molecules in the collision pair since ΔK = 0, ± 2, ± 4 selection rules are needed to account for the Δν1 / 2 ∼ 200 cm−1 bandwidth. The relative intensity of the (1–0) and (0–0) bands indicates that the interaction Hamiltonian is also strongly modulated by the vibrational coordinates of O2. The frequency shift of this simultaneous transition indicates that the intermolecular distance parameter for Δg1···1Δg is 3% larger than for Σg−3···3Σg−. The unusual band shape for the Δg1 + 1Σg+ ← 3Σg− + 3Σg− band is interpreted in terms of an exiton interaction for the Δg1···1Σg>+ combination. Although bound state (O2)2 molecules undoubtedly exist at low temperatures these data provide no unambiguous spectroscopic evidence of their presence.Keywords
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