Solvatochromic shift of the 0-0 phosphorescence band and change of polarizability in the a 1δg → X 3Σ g? -transition in the oxygen molecule

We used known experimental data to analyze the influence of intermolecular interactions on the position of the 0-0-band a¹Δ_g → X³Σ _g ⁻ phosphorescence of molecular oxygen in solutions. A bathochromic (red) shift caused by dispersion interactions and fluctuations of the internal electric field (induction effect) is analyzed employing new formulas obtained by us in the framework of the Onsager model. The contributions from intermolecular repulsion and higher multipole interactions to the shift of the spectrum are also discussed. It is found that the polarizability in the a¹Δ_g state is higher than in the X³Σ _g ^t- state by 0.19 ± 0.03 ų. Taking into account the induced nature of O₂ phosphorescence in solutions, it is noted that the change of polarizability Δα_eg = 0.19 ų should differ from the change of Δα_eg inherent in free molecular oxygen. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 4, pp. 453–459, July–August, 2007.