Photoinduced large amplitude motion as mechanism for pure electronic dephasing and its manifestation in continuous-wave and time-resolved spectroscopy

Abstract

It is demonstrated that photoinduced large amplitude (LA) dynamics on a picosecond time scale may result in electronic pure dephasing on a time scale of a few tens of femtoseconds. It is shown that LA photodynamics affects continuous-wave (cw) spectra (e.g., absorption and resonance-Raman) and transient spectra (e.g., photon-echo and pump–probe) in a rather different way. Calculations are presented for a two-dimensional model problem, consisting of a fast vibrational mode and a slow LA mode, which is considered as a simple model for isomerization. The spectroscopic signals for this model are compared to the results for a complementary model, where the fast vibrational mode interacts with a bath (e.g., the environment). It is shown that standard cw techniques such as absorption and resonance-Raman spectroscopy fail to clearly distinguish the two (physically rather different) model problems, as the ultrafast optical dephasing results in strong line broadening of these spectra. Time-resolved pump–probe spectroscopy, on the other hand, is not limited by electronic pure dephasing and thus allows for a clear discrimination of the two photophysical processes. Simulations of photon-echo experiments furthermore elucidate that slow intramolecular LA motion results in inhomogeneous broadening of optical spectra. Finally a novel time-resolved technique is proposed that is capable to reveal ‘‘sub-linewidth’’ information on electronic transitions which are strongly broadened by homogeneous and inhomogeneous pure dephasing processes.