Nonadiabatic excited-state intramolecular proton transfer in 3-hydroxyflavone: S2 state involvement via multi-mode effect. 2019

Neethu Anand, and Kai Welke, and Stephan Irle, and Sivaranjana Reddy Vennapusa
Indian Institute of Science Education and Research, Thiruvananthapuram, Maruthamala PO,Vithura, Thiruvananthapuram 695551, India.

The excited-state intramolecular proton transfer process in 3-hydroxyflavone is investigated based on the computed structural parameters and energetics of stationary points of vibronically coupled S1-S2 potential energy surfaces. A conical intersection close to the Franck-Condon point on S1 is identified. The minimum energy of the conical intersection is found to be near-degenerate with the equilibrium minimum of S2. Quantum nuclear wavepacket simulations revealed a small population transfer from the "bright" S1 to "dark" S2 on a time scale shorter than the O-H stretching vibrational period. Such a nonadiabatic transition opens up the possibility of new photophysical and photochemical pathways, including the proton transfer via S2.

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