Theoretical Assessment of Hinge-Type Models for Electron Donors in Reaction Centers of Photosystems I and II as well as of Purple Bacteria.

Hinge-type molecular models for electron donors in reaction centers of Photosystems I and II and purple bacteria were investigated using a two-state computational approach based on frozen-density embedding (FDE). This methodology, dubbed FDE-diab, is known to avoid consequences of the self-interaction error as far as intermolecular phenomena are concerned, which allows a prediction of qualitatively correct spin densities for large biomolecular systems. The calculated spin density distributions are in a good agreement with available experimental results and demonstrated a very high sensitivity to changes in the relative orientation of cofactors and amino acid protonation states. This allows a validation of the previously proposed hinge-type models providing hints on possible protonation states of axial histidine molecules.