A computational study of possible mechanisms of singlet oxygen generation in miniSOG photoactive protein

We report high-level electronic structure calculations of electronic states in the miniSOG (for mini Singlet Oxygen Generator) photoactive protein designed to produce singlet oxygen upon light exposure. We consider a model system with a riboflavin (RF) chromophore. To better understand the photosensitization process, we compute relevant electronic states of the combined oxygen-chromophore system and their couplings. The calculations suggest that singlet oxygen can be produced both by inter-system crossing, via a triplet state of the RF(T1)×O2(3Σ− g ) character as well as by triplet excitation energy transfer via a singlet state of the same character. The calculations also suggest a pathway for the production of the triplet state of the chromophore via internal conversion facilitated by oxygen. Our results provide concrete support to previously hypothesized scenarios.