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Low-energy spectrum of iron–sulfur clusters directly from many-particle quantum mechanics

Nature Chemistry volume 6, pages 927–933 (2014)Cite this article

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Abstract

Iron–sulfur clusters are a universal biological motif. They carry out electron transfer, redox chemistry and even oxygen sensing, in diverse processes including nitrogen fixation, respiration and photosynthesis. Their low-lying electronic states are key to their remarkable reactivity, but they cannot be directly observed. Here, we present the first ever quantum calculation of the electronic levels of [2Fe–2S] and [4Fe–4S] clusters free from any model assumptions. Our results highlight the limitations of long-standing models of their electronic structure. In particular, we demonstrate that the widely used Heisenberg double exchange model underestimates the number of states by one to two orders of magnitude, which can conclusively be traced to the absence of Fe dd excitations, thought to be important in these clusters. Furthermore, the electronic energy levels of even the same spin are dense on the scale of vibrational fluctuations and this provides a natural explanation for the ubiquity of these clusters in catalysis in nature.

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Figure 1: Model clusters and many-electron wavefunctions used in this work.
Figure 2: Ab initio levels of [Fe2S2(SCH3)4]2− and corresponding model fits.
Figure 3: Ab initio levels of [Fe2S2(SCH3)4]3− and corresponding model fits.
Figure 4: Origin of the dense manifold in the reduced dimer.
Figure 5: Spin pairings in the [4Fe–4S] cluster.
Figure 6: Energy levels of the [4Fe–4S] cluster.

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Acknowledgements

Work performed by S.S. and G.K.C. was supported by the US National Science Foundation (CHE-1265277) using software developed with the support of OCI-1265278. F.N. and K.S. acknowledge financial support from the Max Planck Society, the University of Bonn and the SFB 813 ‘Chemistry at Spin Centers’.

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Authors and Affiliations

  1. Department of Chemistry, Princeton University, Princeton, 08544-1009, New Jersey, USA

    Sandeep Sharma & Garnet Kin-Lic Chan

  2. Max Planck Institute for Chemical Energy Conversion, Mülheim, 45470, Germany

    Kantharuban Sivalingam & Frank Neese

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  1. Sandeep Sharma
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  2. Kantharuban Sivalingam
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Contributions

S.S. performed the DMRG calculations, analysed the results and contributed to writing the manuscript. F.N. contributed to writing the manuscript. K.S. performed geometry optimization for the [4Fe–4S] model cluster. G.K.C. wrote the manuscript and contributed to the calculations and analysis of the results. All authors discussed the results and commented on the manuscript.

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Correspondence to Garnet Kin-Lic Chan.

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Sharma, S., Sivalingam, K., Neese, F. et al. Low-energy spectrum of iron–sulfur clusters directly from many-particle quantum mechanics. Nature Chem 6, 927–933 (2014). https://doi.org/10.1038/nchem.2041

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