Abstract
A simple, yet powerful wave function manipulation method was introduced utilizing a generalized ionic fragment approach that allows for systematic mapping of the wave function space for multispin systems with antiferromagnetic coupling. The use of this method was demonstrated for developing ground state electronic wave function for [2Fe‐2S] and [Mo‐3Fe‐4S] clusters. Using well‐defined ionic wave functions for ferrous and ferric irons, sulfide, and thiolate fragments, the accuracy of various density functionals and basis sets including effective core potentials were evaluated on a [4Fe‐4S] cluster by comparing the calculated geometric and electronic structures with crystallographic data and experimental atomic spin densities from X‐ray absorption spectroscopy, respectively. We found that the most reasonable agreement for both geometry and atomic spin densities is obtained by a hybrid functional with 5% HF exchange and 95% density functional exchange supplemented with Perdew's 1986 correlation functional. The basis set seems to saturate only at the triple‐ζ level with polarization and diffuse functions. Reasonably preoptimized structures can be obtained by employing computationally less expensive effective core potentials, such as the Stuttgart–Dresden potential with a triple‐ζ valence basis set. The extension of the described calibration methodology to other biologically important and more complex iron–sulfur clusters, such as hydrogenase H‐cluster and nitrogenase FeMo‐co will follow. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 1385–1397, 2006