The lifetime of interatomic Coulombic decay (ICD) [L. S. Cederbaum et al., Phys. Rev. Lett. 79, 4778 (1997)] in Ne2 is determined via an extreme ultraviolet pump-probe experiment at the Free-Electron Laser in Hamburg. The pump pulse creates a 2s inner-shell vacancy in one of the two Ne atoms, whereupon the ionized dimer undergoes ICD resulting in a repulsive Ne+(2p(-1))-Ne+(2p(-1)) state, which is probed with a second pulse, removing a further electron. The yield of coincident Ne+-Ne2+ pairs is recorded as a function of the pump-probe delay, allowing us to deduce the ICD lifetime of the Ne2(+)(2s(-1)) state to be (150±50) fs, in agreement with quantum calculations.
Observing the crucial first few femtoseconds of photochemical reactions requires tools typically not available in the femtochemistry toolkit. Such dynamics are now within reach with the instruments provided by attosecond science. Here, we apply experimental and theoretical methods to assess the ultrafast nonadiabatic vibronic processes in a prototypical complex system—the excited benzene cation. We use few-femtosecond duration extreme ultraviolet and visible/near-infrared laser pulses to prepare and probe excited cationic states and observe two relaxation timescales of 11 ± 3 fs and 110 ± 20 fs. These are interpreted in terms of population transfer via two sequential conical intersections. The experimental results are quantitatively compared with state-of-the-art multi-configuration time-dependent Hartree calculations showing convincing agreement in the timescales. By characterising one of the fastest internal conversion processes studied to date, we enter an extreme regime of ultrafast molecular dynamics, paving the way to tracking and controlling purely electronic dynamics in complex molecules.
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