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M-superoxide intermediate. Therefore, this end-on superoxide species is likely comparable to or slightly less reactive than the side-on superoxide species, not considering the steric effects of their different binding geometries.
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M-OOH intermediate is sterically inaccessible, it is a unlikely pathway.
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1942439573
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The positions of α-carbons of Met/His ligands were kept frozen during the optimizations. The orientation of the FmG substrate was also fixed by freezing the relative angles and dihedrals of all heavy atoms relative to the Met/His α-carbons, except for the two oxygen atoms of the carboxylate group, to reduce the computational cost. The constraints on the substrate FmG in the PES calculations should have a very small effect on the overall energetics because the constrained angles and dihedrals changed little in geometry optimizations of isolated molecules (Figure S1C-E, Supporting Information).
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41
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1942535651
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The difference in ΔE between the PES calculations and the energetics calculations with isolated molecules is due to the slight geometry differences and different intermolecular interactions among the reactants and products.
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