Collision-induced b¹Σ_g⁺–a¹ Δ_g, b¹Σ_g⁺–X³ Σ_g^- and a¹Δ_g–X³Σ_g ^- transition probabilities in molecular oxygen

Abstract

Multireference configuration interaction (MRCI) calculations have been performed for the dipole transition moments of the Noxon band, b¹Σ_g⁺–a¹ Δ_g, and for the red and IR atmospheric emission bands, b¹Σ_g⁺–X³ Σ_g^- and a¹Δ_g–X³Σ_g ^-, in O₂ in collision complexes with different solvent molecules. The spin–orbit coupling between the b¹Σ_g⁺ and X³Σ_g^-(M_S =0) states does not change after collision so the a–X transition borrows intensity from the collision-induced Noxon band b–a, and the b–X band borrows electric dipole transition probability from the collision-induced difference dipole moments of the b and X states. The calculations show that the b–a, a–X and b–X transition probabilities are enhanced by ca. 10⁵, 10³ and 1.2 times by O₂+H₂ collisions. An additional order of magnitude enhancement for all three transitions is possible for solvent molecules with larger polarizability than that of molecular hydrogen. The collision-induced b–a transition dipole moment depends not only on the intermolecular distance, but also on the internuclear O–O distance. Since a–X and b–a transition moments are directly connected (D_a,X=0.013iD_b,a), the strong dependence on the O₂ bond length leads to an additional enhancement of the (0,1) vibronic band intensity of the a¹Δ_g–X³Σ_g ^- transition. The dipole moments of the b and X states are also shown to depend on the O₂ bond length in the collision complex, which leads to additional collision-induced enhancement of the (0,1) band of the b–X system.

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