Diffusional fluorescence quenching of aromatic hydrocarbons.

The quenching of the fluorescence of five aromatic hydrocarbons by three halogenated organics and by molecular oxygen has been measured. Both fluorescence intensity and fluorescence lifetime measurements have been employed to validate results and interpretation; linear Stern-Volmer analyses are shown to apply throughout. The fluorescence quenching rate constant of molecular oxygen for the five aromatic hydrocarbons is essentially equivalent to the diffusion rate constant independent of the fluorophore excitation energy. The halogenated organic-fluorophore rate constants vary by a factor of 965 and are shown to correlate roughly with the energy difference between the quencher and fluorophore excited electronic states in accord with a standard model of quantum two-level mixing. The value of the coupling interaction energy is approximately 2500 cm(-1).