Insights into PSII’s S3YZ• State: An Electronic and Magnetic Analysis

Using BS-DFT (broken-symmetry density functional theory), the electronic and magnetic properties of the S ₃Y _Z ^• state of photosystem II were investigated and compared to those of the S ₃ state. While the O5 oxo-O6 hydroxo species presents little difference between the two states, a previously identified [O5O6] ^3- exhibits reduced stabilization of the O5-O6 shared spin. This species is shown to have some coupling with the Y _Z ^• center through Mn ₁ and O6. Similarly, a peroxo species is found to exhibit significant exchange couplings between the Y _Z ^• center and the Mn cluster through Mn ₁. Mechanistic changes in O-O bond formation in S ₃Y _Z ^• are highlighted by analysis of IBOs (intrinsic bonding orbitals) showing deviation for Mn ₁ and O6 centered IBOs. This change in coupling interactions throughout the complex as a result of S ₃Y _Z ^• formation presents implications for the determination of the mechanism spanning the end of the S ₃ and the start of the S ₄ states, affecting both electron movement and oxygen bond formation.