TY - JOUR
T1 - Nonadiabatic quantum dynamics of the coherent excited state intramolecular proton transfer of 10-hydroxybenzo[h]quinoline
AU - Picconi, David
N1 - Funding Information:
The author thanks the scientific committee of the International Conference on Photochemistry, held (virtually) in Geneva in July 2021, for giving him the opportunity to present the results of the present work at the conference. The author thanks Prof. Dr. Peter Saalfrank for carefully reading this manuscript before submission and for his continuous support. Financial support by the Deutsche Forschungsgemeinschaft (DFG project ME 4215/2–3) is gratefully acknowledged.
Publisher Copyright:
© 2021, The Author(s).
PY - 2021/11
Y1 - 2021/11
N2 - 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.]
AB - 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.]
KW - Coherences
KW - Excited state proton transfer
KW - Nonadiabatic effects
KW - Quantum dynamics
KW - Spectroscopy
UR - http://www.scopus.com/inward/record.url?scp=85117599327&partnerID=8YFLogxK
U2 - 10.1007/s43630-021-00112-z
DO - 10.1007/s43630-021-00112-z
M3 - Article
C2 - 34657277
AN - SCOPUS:85117599327
SN - 1474-905X
VL - 20
SP - 1455
EP - 1473
JO - Photochemical and Photobiological Sciences
JF - Photochemical and Photobiological Sciences
IS - 11
ER -