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

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 S-S potential energy surfaces. A conical intersection close to the Franck-Condon point on S is identified. The minimum energy of the conical intersection is found to be near-degenerate with the equilibrium minimum of S. Quantum nuclear wavepacket simulations revealed a small population transfer from the "bright" S to "dark" S 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 S.