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Low-energy spectrum of iron-sulfur clusters directly from many-particle quantum mechanics
- Publication Year :
- 2014
-
Abstract
- FeS 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. The low-lying electronic states are key to their remarkable reactivity, but 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 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 1-2 orders of magnitude, which can conclusively be traced to the absence of Fe d$\rightarrow$d excitations, thought to be important in these clusters. Further, 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 nature for catalyzing reactions.<br />Comment: Nature Chemistry, 2014
Details
- Database :
- arXiv
- Publication Type :
- Report
- Accession number :
- edsarx.1408.5080
- Document Type :
- Working Paper
- Full Text :
- https://doi.org/10.1038/nchem.2041