Abstract
The luminescence of singlet molecular oxygen (1Δg or 1O2) caused by the 1Δg → 3Σg− transition in liquid saturated hydrocarbons from n-hexane to n-undecane is investigated. A model of quenching of the 1Δg state of the oxygen molecule by the CH oscillations of the molecules of solvents is proposed, in which the rate constant of the nonradiative deactivation (knr) depends strongly on the average distance between the 1O2 and CH groups of the solvent. This experimental dependence can adequately be described by an exponential function with the distance parameter R0 = 0.15 A, which indicates that the acceleration of quenching with the solvent density is a result of larger overlapping of the electron orbitals of oxygen and the CH groups. The detected increase in knr with temperature can also be explained qualitatively well within the framework of the model suggested. It is shown that the radiative rate constant (kr of the 1Δg → 3Σg− transition does not depend on the distance between the 1O2 and CH groups and its change in a number of hydrocarbons is related to macroscopic parameters, in particular, the polarizability of the solvent.
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