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Entangled quantum electronic wavefunctions of the Mn_4CaO_5 cluster in photosystem II

Kurashige, Yuki and Chan, Garnet Kin-Lic and Yanai, Takeshi (2013) Entangled quantum electronic wavefunctions of the Mn_4CaO_5 cluster in photosystem II. Nature Chemistry, 5 (8). pp. 660-666. ISSN 1755-4330. doi:10.1038/nchem.1677.

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It is a long-standing goal to understand the reaction mechanisms of catalytic metalloenzymes at an entangled many-electron level, but this is hampered by the exponential complexity of quantum mechanics. Here, by exploiting the special structure of physical quantum states and using the density matrix renormalization group, we compute near-exact many-electron wavefunctions of the Mn_4CaO_5 cluster of photosystem II, with more than 1 × 10^(18) quantum degrees of freedom. This is the first treatment of photosystem II beyond the single-electron picture of density functional theory. Our calculations support recent modifications to the structure determined by X-ray crystallography. We further identify multiple low-lying energy surfaces associated with the structural distortion seen using X-ray crystallography, highlighting multistate reactivity in the chemistry of the cluster. Direct determination of Mn spin-projections from our wavefunctions suggests that current candidates that have been recently distinguished using parameterized spin models should be reassessed. Through entanglement maps, we reveal rich information contained in the wavefunctions on bonding changes in the cycle.

Item Type:Article
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URLURL TypeDescription ReadCube access
Kurashige, Yuki0000-0003-4652-8153
Chan, Garnet Kin-Lic0000-0001-8009-6038
Alternate Title:Entangled quantum electronic wavefunctions of the Mn4CaO5 cluster in photosystem II
Additional Information:© 2013 Macmillan Publishers Limited. Received 09 November 2012 | Accepted 03 May 2013 | Published online 09 June 2013. Y.K. and T.Y. were supported in part by a Grant-in-Aid for Scientific Research (C) (grant no. 25410030) and a Grant-in-Aid for Scientific Research (B) (grant no. 25288013), respectively, from MEXT, Japan. Y.K. and T.Y. acknowledge support from the Institute for Molecular Science and a grant of CPU time from the Research Center for Computational Science. G.K-L. Chan was supported by the US Department of Energy, Office of Science (DE-FG02-07ER46432).
Funding AgencyGrant Number
Ministry of Education, Culture, Sports, Science and Technology (MEXT)25410030
Ministry of Education, Culture, Sports, Science and Technology (MEXT)25288013
Institute for Molecular ScienceUNSPECIFIED
Department of Energy (DOE)DE-FG02-07ER46432
Issue or Number:8
Record Number:CaltechAUTHORS:20170126-090717197
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:73750
Deposited By: Donna Wrublewski
Deposited On:26 Jan 2017 17:20
Last Modified:11 Nov 2021 05:21

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