Photoinduced breaking of the Fe–O$_{2}$ bond in hemoglobin: dissociation quantum yield, excited electronic states, and nonradiative relaxation processes
Abstract:
Bimolecular recombination of molecular oxygen with human hemoglobin upon excitation in different spectral ranges is studied by nanosecond laser kinetic spectroscopy. The results obtained are fundamentally different; i.e., rather efficient photodissociation takes place in the case of excitation into the $Q$-band of the $\pi\pi$* nature and is practically absent upon excitation into the near-IR band corresponding to the electron transfer from the porphyrin $a_{2u}$ orbital to a mixed orbital formed of the iron $d$ orbital and the free $\pi$ orbital of molecular oxygen. Analysis of these data, together with data obtained previously using the techniques of nano-, pico-, and femtosecond spectroscopy, allowed us to describe the mechanism and dynamics of the photodissociation reaction and intraheme relaxation processes.