Ultrafast Internal Conversion Dynamics through the on-the-Fly Simulation of Transient Absorption Pump-Probe Spectra with Different Electronic Structure Methods.

An on-the-fly surface-hopping simulation protocol is developed for the evaluation of transient absorption (TA) pump-probe (PP) signals of molecular systems exhibiting internal conversion to the electronic ground state. We study the nonadiabatic dynamics of azomethane and the associating TA PP spectra at three levels of the electronic-structure theory, OM2/MRCI, SA-CASSCF, and XMS-CASPT2. The impact of these methods on the population dynamics and time-resolved TA PP signals is substantially different. This difference is attributed to the strong non-Condon effects that must be taken into account for the proper understanding and interpretation of time-resolved TA PP signals of nonadiabatic polyatomic systems. This shows that the combination of the dynamical and spectral simulations definitely provides more accurate and detailed information on the microscopic mechanisms of photophysical and photochemical processes. Hence the simulation of time-resolved spectroscopic signals provides another important dimension to examine the accuracy of quantum chemistry methods.