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

Sharma, S., Sivalingam, K., Neese, F., & Chan, G.-K.-L. (2014). Low-energy spectrum of iron–sulfur clusters directly from many-particle quantum mechanics. Nature Chemistry, 6(10), 927-933. doi:10.1038/nchem.2041.

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 Creators:
Sharma, Sandeep1, Author
Sivalingam, Kantharuban2, Author              
Neese, Frank2, Author              
Chan, Garnet Kin-Lic1, Author
Affiliations:
1Department of Chemistry, Princeton University, Princeton, 08544-1009, New Jersey, USA, ou_persistent22              
2Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              

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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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Language(s): eng - English
 Dates: 2013-12-022014-07-242014-08-312014-10-01
 Publication Status: Published in print
 Pages: 7
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1038/nchem.2041
 Degree: -

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Title: Nature Chemistry
  Abbreviation : Nat. Chem.
Source Genre: Journal
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Publ. Info: London, UK : Nature Publishing Group
Pages: - Volume / Issue: 6 (10) Sequence Number: - Start / End Page: 927 - 933 Identifier: ISSN: 1755-4330
CoNE: https://pure.mpg.de/cone/journals/resource/1755-4330