2014/08/21 by Sandeep Sharma, Kantharuban Sivalingam, Frank Neese +1 · 1 citation
Physics and Astronomy · #cond-mat.mtrl-sci #cond-mat.str-el #physics.bio-ph #physics.chem-ph #physics.comp-ph
paper · pdf · doi:10.1038/nchem.2041
Nature Chemistry, 2014
arxiv created 2014/08/21 · arxiv updated 2015/06/22
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→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.