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Time-resolved photoelectron spectroscopy of non-adiabatic electronic dynamics in gas and liquid phases

Time-resolved photoelectron spectroscopy of non-adiabatic processes in isolated molecules in molecular beams and aqueous solutions at ambient temperatures is discussed. In the former, time–energy mapping of photoelectron kinetic energy and angular distributions is performed with 22 fs time-resolution by photoelectron imaging using a multicolour filamentation light source. The S 2–S 1 internal conversion dynamics in pyrazine, benzene and toluene mediated by conical intersections and deactivation of furan from the Rydberg and valence states are discussed. In the latter, a liquid beam photoelectron spectrometer (hemispherical or time-of-flight) is coupled with a sub-MHz non-collinear optical parametric amplifier. Additionally, charge-transfer-to-solvent reactions from I− to polar protic solvents are observed, and the vertical electron binding energies of solvated electrons in bulk solutions are determined.