Effect of Solvent on the O2(a(1)Δg) → O2(b(1)Σg(+)) Absorption Coefficient.

Radiative transitions between the three lowest-lying electronic states of molecular oxygen have long provided a model to study how collision-dependent perturbations influence forbidden processes. In an isolated oxygen molecule, transitions between the O2(X(3)Σg(-)), O2(a(1)Δg), and O2(b(1)Σg(+)) states are forbidden as electric-dipole processes. For oxygen dissolved in organic solvents, the probabilities of radiative transitions between these states increase appreciably. Attempts to interpret solvent-dependent changes in the radiative rate constants have principally relied on O2(b(1)Σg(+)) and O2(a(1)Δg) emission experiments. However, the dominant nonradiative deactivation channels of O2(b(1)Σg(+)) make it difficult to quantify solvent effects on the O2(b(1)Σg(+)) → O2(a(1)Δg) radiative process. Thus, an appreciable amount of important information has heretofore not been available. In the present study, we examined the effect of 17 common organic solvents on the O2(a(1)Δg) → O2(b(1)Σg(+)) absorption transition at ∼5200 cm(-1) (i.e., ∼1925 nm). The solvent-dependent absorption coefficients at the band maximum, εmax, range from 5 to 50 M(-1) cm(-1) and correlate reasonably well with the solvent refractive index; εmax is largest in solvents with the largest refractive index. This observation is consistent with a model in which oxygen is perturbed to a greater extent by solvents with a large electronic polarizability. Through the Strickler-Berg equation, we also used these absorption data to obtain the radiative rate constant for the O2(b(1)Σg(+)) → O2(a(1)Δg) transition, and the results are consistent with a model in which the O2(a(1)Δg) → O2(X(3)Σg(-)) transition is said to steal intensity from the O2(b(1)Σg(+)) → O2(a(1)Δg) transition.