Femtosecond pump–probe photoelectron spectroscopy on Na2: a tool to study basic coherent control schemes

Abstract.

Femtosecond pump–probe photoelectron spectroscopy has become a common tool in ultrafast gas-phase science because of its sensitivity both to structural and electronic changes in a molecule upon excitation. Here a summary and extended discussion of our experiments is presented. We focus on the potential of this method to study basic femtosecond coherent control schemes. Multi-photon excitation of the Na₂ molecule with femtosecond laser pulses leads to preparation of vibrational wave packets. Mapping of the vibrational wave-packet dynamics by time-resolved photoelectron spectroscopy offers the high spatial and temporal resolution required to investigate a variety of laser-control parameters in great detail. Besides an illustration of the Tannor–Kosloff–Rice scheme we demonstrate electronic transitions at Franck–Condon forbidden internuclear distances due to the intensity of the applied laser pulses. Further we discuss the influence of simple phase-modulated (linearly chirped) laser pulses on a molecular multi-photon process. An enhanced population transfer is derived due to synchronization of the wave-packet motion on an electronic potential to an appropriate chirp of the laser pulses. In addition, the influence of the temporal profile on the population transfer and the role of the pulse duration are studied.