Stepwise Excited-State Intramolecular Double Proton Transfer in 1,8-Dihydroxynaphthalene-2,7-dicarbaldehyde

We theoretically investigate the salient features of stepwise excited-state intramolecular double proton transfer (ESIDPT) in 1,8-dihydroxynaphthalene-2,7-dicarbaldehyde (DHDA). Surface trajectory simulations using the TD-B3LYP/6-31G(d) level of theory reveal that the proton transfer primarily happens via S₁, wherein about ∼42% of trajectories (40 out of 95) show the single proton transfer alone and another ∼32% (30 out of 95) show double proton transfer. The average time scale for the single proton transfer originating from those ∼42% trajectories is ∼147 fs. In the case of double proton transfer, the average time for the first step, i.e., single proton transfer, is ∼54 fs, and the subsequent step, i.e., double proton transfer, completes in ∼151 fs. All three tautomers, i.e., normal, single, and double proton-transferred tautomers, possess a stable minimum in their first singlet excited state. This state has a ππ* character in the former two tautomers, resulting in a dual fluorescence emission phenomenon upon photoexcitation of DHDA.