Insights into PSII's S 3 Y Z • State: An Electronic and Magnetic Analysis

Using BS-DFT (broken-symmetry density functional theory), the electronic and magnetic properties of the S Y state of photosystem II were investigated and compared to those of the S state. While the O5 oxo-O6 hydroxo species presents little difference between the two states, a previously identified [...

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Published in:The journal of physical chemistry letters 2024-01, Vol.15 (2), p.499-506
Main Authors: Rummel, Felix, Malcomson, Thomas, Barchenko, Maxim, O'Malley, Patrick J
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Language:English
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description Using BS-DFT (broken-symmetry density functional theory), the electronic and magnetic properties of the S Y state of photosystem II were investigated and compared to those of the S state. While the O5 oxo-O6 hydroxo species presents little difference between the two states, a previously identified [O5O6] exhibits reduced stabilization of the O5-O6 shared spin. This species is shown to have some coupling with the Y center through Mn and O6. Similarly, a peroxo species is found to exhibit significant exchange couplings between the Y center and the Mn cluster through Mn . Mechanistic changes in O-O bond formation in S Y are highlighted by analysis of IBOs (intrinsic bonding orbitals) showing deviation for Mn and O6 centered IBOs. This change in coupling interactions throughout the complex as a result of S Y formation presents implications for the determination of the mechanism spanning the end of the S and the start of the S states, affecting both electron movement and oxygen bond formation.
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title Insights into PSII's S 3 Y Z • State: An Electronic and Magnetic Analysis
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