Collisional depolarization of fluorescence of polyatomic molecules in the gas phase by excited state quenchers

Abstract

A new method of extracting information on the efficiencies of quenching of an excited state and collisional reorientation from the data on the fluorescence depolarization of molecular vapors by quenchers of the excited state is proposed. The method does not involve collisional cross sections and fluorescence lifetimes. From the experimental data on the depolarization of polarized luminescence of para-quaterphenyl and 2-(4′-dimethylamine) phenyl-5-phenyloxydiazole by oxygen and nitrogen, the ratios of the constants of the excitedstate quenching and orientation randomization (fluorescence depolarization) by oxygen are obtained. For these molecules, the probabilities of the excited-state quenching q and orientation randomization s per collision with oxygen molecules are determined (q=0.25±0.04 and s=0.13±0.04 for para-quaterphenyl and q=0.2±0.04 and s=0.21±0.04 for 2-(4′-dimethylamine)phenyl-5-phenyloxydiazole). The self-quenching of fluorescence of perylene vapors, with the probability 0.28 per collision, is found.