Excited State Intramolecular Proton Transfer of 1-Hydroxyanthraquinone

Abstract

The excited state intra-molecular proton transfer dynamics of 1-hydroxyanthraquinone in solution are investigated by femtosecond transient absorption spectroscopy and quantum chemistry calculations. Two characteristic bands of excited state absorption and stimulated emission are observed in transient absorption spectra with the excitation by the pump wavelength of 400 nm. From the delayed stimulated emission signal, the time scale of the intra-molecular proton transfer is determined to be about 32 fs. The quantum chemistry calculations show that the molecular orbits and the order of the S2 and S1 states are reversal and a conical intersection is demonstrated to exist along the proton transfer coordinate. After proton transfer, the second excited state of tautomer populated via the conical intersection undergoes the internal conversion with ∼200 fs and the following intermolecular energy relaxation with ∼16 ps. The longer component 300 ps can be explained in terms of the relaxation from excited-state tautomer to its ground state. From our observations, two proton transfer pathways via a conical intersection are proposed and the dominated one preserves the molecular orbits.