Coherent vibrational dynamics in molecular bond breaking: methyl radical umbrella mode probed by femtosecond x-ray spectroscopy

We report on the observation of coherent molecular vibrations launched by the breaking of a molecular bond. The methyl radical, which is produced by $267\,\mathrm{nm}$ photodissociation of methyl iodide, is excited to high levels in its $ν_2$ ``umbrella" vibrational mode by the dissociation. The ensuing coherent vibrational dynamics are observed by measuring ultrafast time-dependent changes in the x-ray transition energy from the C$1s$ to the singly-occupied valence orbital. Due to symmetry, the real space vibrational motion appears predominantly in the x-ray energy shift at the difference frequencies of the $ν_2$ progression, although the fundamental frequencies of the $ν_2$ mode are also observed. By constructing a fully quantum-mechanical model of the dynamics the coherent superposition is rigorously characterized and the real-space motion of the radicals is reconstructed. The retrieved trajectories are dominated by pronounced quantum beating governed by the high degree of coherent excitation and the strong negative anharmonicity of the $ν_2$ mode.