Abstract
The intracluster reaction initiated in Ba⋯FCH 3 by excitation to its electronic B̃ state near 540 nm proceeds on an extremely short timescale. A time constant of (70±10) fs is deduced for the rate-determining step in Ba⋯FCH 3 whereas for the deuterated complex Ba⋯FCD 3 this time is enlarged to (100±10) fs. By comparison with the results obtained for the reaction via the excited à state at 618 nm a reaction model is suggested which explains the BaF product formation in two successive steps.
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