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Because we have used the unrestricted Kohn-Sham (KS) formalism, the resulting KS determinants are not eigenfunctions of the Ŝ 2 operator. While the deviation from the pure S, 3/2 (or S, 1 for peroxy) states is negligible for the ferromagnetically coupled states, the antiferromagnetically coupled states deviate significantly from pure S, 1/2 (or S, 0) states, which can only be described by multireference wave functions. Nevertheless, this approach is routinely used in the studies of antiferromagnetically coupled model complexes representing metal sites in proteins. The reported values are unrestricted DFT energies without spin projection. The broken-symmetry technique can be used to correct the energies of the antiferromagnetically coupled (AF) states, viz. E AF, EF, 3/2(EF, E BS) for all three coppers coupled and EAF, EF
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