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Studies of the flash photolysis of heme‐bearing proteins have often assessed the role of ligand diffusion in very approximate ways and a disagreement about the importance of ligand diffusion exists in the literature as a result. This paper provides a somewhat more sytematic analysis of diffusional effects than has been given previously for the simple case of ligand–protoheme binding. The model developed here is fit to the available data for the ligand CO in glycerol–water solvents. The fit suggests that diffusional motions become important for the kinetics of this system for temperatures below 270 K and that these motions are strongly correlated when the reactants are close through interactions with the solvent.

The role of diffusion in the binding of carbon monoxide to protoheme in high-viscosity solvents