Comparison of Experimental and Broken Symmetry Density Functional Theory Calculated Electron Paramagnetic Resonance Parameters for the Manganese Catalase Active Site in the Superoxidized Mn^III/Mn^IV State

Broken symmetry density functional theory has been used to calculate g-tensor, ⁵⁵Mn, ¹⁴N, and ¹⁷O hyperfine couplings for active site models of superoxidized Mn^III/Mn^IV manganese catalase both in its native and azide-inhibited form. While a good agreement is found between the calculated and experimental g-tensor and ⁵⁵Mn hyperfine couplings for all models, the active site geometry and Mn ion oxidation state can only be readily distinguished based on a comparison of the calculated and experimental ¹⁴N azide and ¹⁷O HFCs. This comparison shows that only models containing a Jahn-Teller distorted 5-coordinate (Mn^III)₂ site and a 6-coordinate (Mn^IV)₁ site can satisfactorily reproduce the experimental ¹⁴N and ¹⁷O hyperfine couplings.