A proposed new scheme for vibronically resolved time-dependent photoelectron spectroscopy: pump-repump-continuous...

We propose a new scheme for time-resolved photoelectron spectroscopy denoted as pump-repump-continuous wave-photoelectron spectroscopy (prp-cw-pes). This scheme is comprised of two femtosecond laser (pump) pulses under cw illumination (probe). By changing the time-delay between pump and repump lasers one can manipulate the populations of vibronic levels in electronic excited states. The cw laser acts on for a long time and establishes resonance between excited states and the continuum photo-ionized states. Sharp spectra can be obtained from the resonance condition [formula: see text]. The intensities in the spectra are sensitive to the time-delay between the pump-repump pulses, but only depend on the populations of excited states, not the phase relations (coherence). As a result, each time-delayed snapshot spectrum is a weighted sum of so-called fingerprints, where a fingerprint is the vibrationally resolved photoelectron spectrum for a single vibronic excited state. The latter information can potentially be simulated reliably using vibronic models and wave packet propagation methods. In the easiest application of the experiment, different time-delays produce different spectra, for a single molecular system. This wealth of experimental data can be fitted to an, ideally small, set of theoretical fingerprints by adjusting the populations as fitting parameters. This technique might be able to distinguish between closely related molecular species. Adopting a different viewpoint, the proposed scheme can also be employed to monitor the time-dependent dynamics by changing the phase relationship between the pump and repump laser that can be viewed as a "control mechanism" employed in wave packet interferometry. Simplifications arise as the change in the spectra is due to the changing populations, not because of the coherence. In this paper, we outline the ideas behind the scheme and illustrate the ideas theoretically using simple model systems.