Nonadiabatic quantum dynamics of the coherent excited state intramolecular proton transfer of 10-hydroxybenzo[h]quinoline

Abstract

Abstract The photoinduced nonadiabatic dynamics of the enol-keto isomerization of 10-hydroxybenzo[h]quinoline (HBQ) are studied computationally using high-dimensional quantum dynamics. The simulations are based on a diabatic vibronic coupling Hamiltonian, which includes the two lowest $$\pi \pi ^*$$ π π ∗ excited states and a $$n\pi ^*$$ n π ∗ state, which has high energy in the Franck–Condon zone, but significantly stabilizes upon excited state intramolecular proton transfer. A procedure, applicable to large classes of excited state proton transfer reactions, is presented to parametrize this model using potential energies, forces and force constants, which, in this case, are obtained by time-dependent density functional theory. The wave packet calculations predict a time scale of 10–15 fs for the photoreaction, and reproduce the time constants and the coherent oscillations observed in time-resolved spectroscopic studies performed on HBQ. In contrast to the interpretation given to the most recent experiments, it is found that the reaction initiated by $$1\pi \pi ^* \longleftarrow S_0$$ 1 π π ∗ ⟵ S 0 photoexcitation proceeds essentially on a single potential energy surface, and the observed coherences bear signatures of Duschinsky mode-mixing along the reaction path. The dynamics after the $$2\pi \pi ^* \longleftarrow S_0$$ 2 π π ∗ ⟵ S 0 excitation are instead nonadiabatic, and the $$n\pi ^*$$ n π ∗ state plays a major role in the relaxation process. The simulations suggest a mainly active role of the proton in the isomerization, rather than a passive migration assisted by the vibrations of the benzoquinoline backbone. Graphic Abstract