文摘
Photochemical reactions are mediated by conical intersections (CI), which are difficult to directly probe and characterize. To gain insight into CIs, two-dimensional femtosecond stimulated Raman spectroscopy (2D-FSRS) is used to examine a model excited-state charge-transfer (CT) complex consisting of an electron donor, tetramethylbenzene (TMB), and an acceptor, tetracyanoquinodimethane (TCNQ). Following impulsive excitation, the excited-state transient absorption reveals large-amplitude excited-state wave packet motion along low-frequency modes, in particular TCNQ鈥檚 totally symmetric 323 cm鈥? CCN bend, which persist for 5 ps. These low-frequency coherences modulate the intensity and peak frequencies of the excited-state FSRS vibrational spectra. In particular, large-magnitude oscillations at 323 cm鈥? are observed in the peak frequency (螖蠅 = 2 cm鈥?) and intensity (螖OD = 1.5 mOD) of the nontotally symmetric 1271 cm鈥? C鈺怌 rocking mode. The magnitude of these oscillations is analyzed to determine the first-order anharmonic coupling between the high- and low-frequency degrees of freedom in the excited state. The anharmonic coupling between the totally symmetric 323 cm鈥? and the nontotally symmetric 1271 cm鈥? modes is estimated to be in excess of 50 cm鈥?, strongly suggesting that they are the tuning and coupling modes, respectively, for the CI that connects the CT excited state to the neutral ground state and controls charge recombination internal conversion.