Controlling the Nonadiabatic Dynamics of the Charge-Transfer Process with Chirped-Pulses: Insights from a Double-Pump Time-Resolved Fluorescence Spectroscopy Scheme.

The manipulation of the ultrafast quantum dynamics of a molecular system can be achieved through the application of tailored light fields. This has been achieved in many ways in the past. In our present investigations, we show that it is possible to exert specific control over the nonadiabatic dynamics of a generic model system describing ultrafast charge-transfer within a condensed dissipative environment by using frequency-chirped pulses. By adjusting the external photoexcitation conditions, such as the chirp parameter, we show that the final population of the excitonic and charge-transfer states can be significantly altered, thereby influencing the elementary steps controlling the transfer process. Besides, we introduce an excitation scheme based on double-pump time-resolved fluorescence spectroscopy using chirped-pulse excitations. Here, our findings reveal that chirped excitations enhance the vibrational system dynamics as evidenced by the simulated spectra, where a substantial signal intensity dependence on the chirp is observed. Our simulations show that chirped pulses are a promising tool for steering the dynamics of the charge-transfer process towards a desired target outcome.