Kinetics of the b{su1}Σ{sk{su\s+}/{in{itg}}→\ga{su1}\gD{in{itg}} fluorescence of molecular oxygen in solutionsfluorescence of molecular oxygen in solutions

Abstract

The kinetics of sensitized fluorescence of O₂ has been recorded for the first time in solutions at transition from the second singlet excited state b{su1}Σ{sk{su\s+}/{in{itg}} to the first excited state \ga{su1}\gD{in{itg}} (b→a. We measured the quantum yield of the b→a-fluorescence at γ≈1.93 μm and assessed its probability with respect to the a→ X-phosphorescence at 1.27 μm. We show that the lifetime of the b→a-fluorescence (105 nsec for CCl₄ and 140 nsec for CS₂) becomes much shorter on addition of solvents with large frequencies of intramolecular vibrations. The measured radiative velocity constant of the b→a-transition K_b→a is by three orders of magnitude larger than for the phosphorescence (≈1.27 μm) of the a→X-transition from the first singlet to the ground triplet state. The method of recording IR fluorescence is promising for determining O₂ in solutions and biosystems.