Origin of proton induced fluorescence quenching of colloidal carbon dots: reshaping of Schrödinger wavefunctions and huge red shift of transition energy

The fluorescence quenching by protons is a universal phenomenon but the mechanism remains unclear. Here, we take the fluorescent amide-terminated carbon dots as a prototype to study the proton fluorescence quenching mechanism by using both experiments and time-dependent density functional theory calculations. The study reveals that when an approached proton is captured by the weakly negatively charged fluorophore group of the colloidal carbon dot, it will substantially change the electron wavefunctions owing to the strong proton-electron interaction, and this leads to highly diminished energy gap and resultant fluorescence quenching in the visible spectral region. The protons generated by hydrolysis of various types of metal ions also exhibit fruitful fluorescence quenching and the quenching efficiency is roughly proportional to the hydrolysis constant of the metal ion. This fluorescence quenching mechanism is quite distinct from the conventional ones involving electron or energy transfer.