Imaging Reversible and Irreversible Structural Evolution in Photoexcited 2,4-Difluoroaniline

Here, we demonstrate the capability of femtosecond time-resolved photoelectron imaging to visualize the reversible and irreversible structural evolution in electronically excited 2,4-difluoroaniline. As a coherent superposition of out-of-plane vibrational motions is created following 299.8 nm excitation, the molecular geometry alters periodically, thus modulating the photoionization channel. The reversible nuclear motion between distinct geometries is directly observed as the reverse beats in the time-dependent photoelectron spectra. Moreover, with the molecule highly vibrationally excited at 289.0 nm, the exponential decrease/increase changes in photoelectron signal provide a physically intuitive and complete picture of the irreversible geometry rearrangement away from a nonplanar geometry in the vertical Franck-Condon region toward the planar minimum.