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

David Picconi*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

7 Citations (Scopus)

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 ππ excited states and a nπ 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 ππ⟵ S 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 ππ⟵ S excitation are instead nonadiabatic, and the nπ 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: [Figure not available: see fulltext.]

Original languageEnglish
Pages (from-to)1455-1473
Number of pages19
JournalPhotochemical and Photobiological Sciences
Volume20
Issue number11
DOIs
Publication statusPublished - Nov-2021
Externally publishedYes

Keywords

  • Coherences
  • Excited state proton transfer
  • Nonadiabatic effects
  • Quantum dynamics
  • Spectroscopy

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