Excited-state photochemistry dynamics of 2-(1-naphthyl) phenol: electronic structure calculations and non-adiabatic dynamics simulations

Abstract

The excited-state proton transfer processes and the formation mechanism of quinone methide of (1-naphthyl)phenol were investigated by combining static electronic structure calculations and non-adiabatic dynamics simulations in vacuum. The results indicated the existence of two minimum energy structures (S0-ENOL-1 and S0-ENOL-2) in the ground and excited states, which correspond to two ESIPT pathways. Upon excitation of S0-ENOL-1 to the bright S₁ state, the system relaxes to the S₁ minimum quickly in the enol region, for which two decay pathways have been described. The first is a barrierless ESIPT-1 process that generates keto species. Afterwards, the system encounters a keto conical intersection, which funnels the system to the ground state. The generated keto species, in the S₀ state, either regenerated the starting material via ground-state proton transfer or yielded the keto product at the end of the simulations. In the other pathway, the system de-excites from the S₁ state to the S₀ state via one enol-type conical intersection. The dynamics simulations showed that 58.8% of trajectories experience keto-type conical intersection and the rest undergo enol-type conical intersection. Besides the ESIPT-1 process, a new-type ESIPT (ESIPT-2), which was not observed experimentally, was found with the irradiation of S0-ENOL-2. The ESIPT-2 process occurs after overcoming a small barrier (0.9 kcal mol⁻¹) and yields a distinct quinone methide. Our simulation results also showed that the S₁ lifetime of S0-ENOL-1 (S0-ENOL-2) would be 437 (617) fs in the gas phase. These results provide detailed and important mechanistic insights into the systems in which ESPT to carbon atoms occurs.