Calculations of relaxed geometries of multi-centre transition metal compounds are routinely carried out using Broken Symmetry Density Functional Theory. The resulting low-spin open shell electronic state is described by one...

Multicenter transition metal complexes are the key moieties of many processes in chemistry, biochemistry, and materials science such as in the active sites of enzymes, molecular catalysts, and biological electron carriers. Their electronic structure, often characterized by high-spin-polarized metal sites, is a challenge for theoretical chemists because of their high degree of dynamical and static correlation. Static correlation is necessary both for the appropriate description of the metal-ligand bonding and for a correct description of the multideterminant character arising from the magnetic interactions between spin centers. Density functional theory (DFT) is usually applied using a single-determinant broken-symmetry state that is lacking the correct spin symmetry when the ground state has total low-spin character. To alleviate this drawback, we use the extended broken-symmetry (EBS) approach to derive approximate ground-state energies and, for the first time, forces for the correctly symmetric ground state of an arbitrary number of spin centers within the framework of the Heisenberg-Dirac-van Vleck Hamiltonian. Remarkably, the proposed procedure supplies relaxed geometries that are fully consistent with the calculated J-coupling constants. We apply the method to investigate the relaxed geometrical structure of the low-spin ground state of iron-sulfur clusters with two, three, and four iron centers. We observed significant differences in both geometrical parameters and coupling constant J between the symmetrized ground state, the high-spin, and the broken-symmetry optimized structures. These changes are often comparable with the differences observed by using different functionals, and the use of EBS always improves the description of the studied systems. It will be therefore important to include it in any DFT attempt to quantitatively describe multicenter transition metal complexes in the future.

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