Fluorescence Quenching at High Quencher Concentrations

Chemical reactions occurring in dense media at high reactant concentrations can be described by rate ‘‘constants’’ which are actually functions of concentration. We present a theoretical model in which this so‐called rate constant ‘‘renormalization’’ occurs for the specific case of fluorescence quenching in solution. We show that both the quenching and the excitation rate constants can become concentration dependent. We fit our theory to several sets of experimental data—our own and some from the literature—and show that excellent agreement is obtained by varying a single free parameter, namely, the efficiency with which a fluorophore‐quencher collision leads to a quench of the excited state