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Abstract

The impact of altering the solvent pH value on the photodynamic activity of thionine has been studied computationally by means of density functional theory and multi‐reference interaction methods. To this end, we have investigated the electronic structure of the ground and excited states of diprotonated (TH₂²⁺) and neutral imine (T) forms of thionine (TH⁺). It is well known experimentally that the T₁ state of TH⁺ undergoes acid–base equilibrium reactions resulting in a pronounced pH effect for the efficiency of singlet‐oxygen (¹O₂) production. Our results show that the energy‐transfer reactions from the T₁ state of TH₂²⁺ and T to ³O₂ correspond to reversible equilibrium processes, whereas in TH⁺ this process is very exothermic in a vacuum (−0.66 eV) and in aqueous solution (−0.49 eV). These facts explain the experimental observation of a much smaller efficiency of ¹O₂ production for TH₂²⁺ than for TH⁺. Moreover, we found that the pH value significantly effected the intersystem crossing (ISC) kinetics impacting the concentration of triplet‐state species available for energy transfer. In very acidic aqueous solution (pH<2) where TH₂²⁺ is the prevailing species, the ISC proceeds with a rate constant of ≈10⁸ s⁻¹. In a basic medium where T is the dominant species, ISC decay occurs by means of a thermally activated channel (≈10⁸ s⁻¹) which competes with fluorescence (5.32×10⁷ s⁻¹). According to these results, maximum ISC efficiency is expected for intermediate acidic pH values (TH⁺, ≈10⁹ s⁻¹).