Insights into Ultrafast Relaxation Dynamics of Electronically Excited Furfural and 5-Methylfurfural

The ultrafast relaxation dynamics of furfural and 5-methylfurfural following excitation in the ultraviolet range is investigated using the femtosecond time-resolved photoelectron spectroscopy method. Specifically, the pump wavelength-dependent decay dynamics of electronically excited furfural and 5-methylfurfural is discussed on the basis of a detailed analysis of our measured time-resolved photoelectron spectroscopy spectra. Irradiation at all pump wavelengths prepares both furfural and 5-methylfurfural molecules with different vibrational levels in the first optically bright S₂ (¹ππ*) state, the lifetime of which is measured to be at least hundreds of femtoseconds. Besides the prominent deactivation channels of ring-opening and ring-puckering pathways for the S₂(¹ππ*) state, we propose that there is a minor decay channel of internal conversion from the initially prepared S₂(¹ππ*) state to the S₁(¹nπ*) state. The wavepacket decays out of the Franck-Condon region on the S₂(¹ππ*) state potential energy surface and bifurcates into different parts somewhere. A small fraction of the wavepacket funnels down to the S₁(¹nπ*) state via internal conversion. The subsequently populated S₁(¹nπ*) state contains large vibrational excess energy and decays over a lifetime of 2.5-2.8 ps. One of the deactivation channels of the S₁(¹nπ*) state is intersystem crossing to the ³ππ* triplet state. In addition, methyl substitution effects on the excited-state dynamics of furfural are also discussed. This experimental study provides new insights into the excitation energy-dependent decay dynamics of photoexcited furfural and 5-methylfurfural.