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Disentangling the dynamics of electrons and nuclei during nonadiabatic molecular transformations remains a considerable experimental challenge. Here we have investigated photoinduced electron transfer dynamics following a metal-to-ligand charge-transfer (MLCT) excitation of the [Fe(bmip)2]2+ photosensitizer, where bmip = 2,6-bis(3-methyl-imidazole-1- ylidine)-pyridine, with simultaneous femtosecond-resolution Fe K{\alpha} and K\b{eta} X-ray Emission Spectroscopy (XES) and Wide Angle X-ray Scattering (WAXS). This measurement clearly shows temporal oscillations in the XES and WAXS difference signals with the same 278 fs period oscillation. The oscillatory signal originates from an Fe-ligand stretching mode vibrational wavepacket on a triplet metal-centered (3MC) excited state surface. The vibrational wavepacket is created by 40% of the excited population that undergoes electron transfer from the non-equilibrium MLCT excited state to the 3MC excited state with a 110 fs time constant, while the other 60% relaxes to a 3MLCT excited state in parallel. The sensitivity of the K{\alpha} XES spectrum to molecular structure results from core-level vibronic coupling, due to a 0.7% average Fe-ligand bond length difference in the lowest energy geometry of the 1s and 2p core-ionized states. These results highlight the importance of vibronic effects in time-resolved XES experiments and demonstrate the role of metal-centered excited states in the electronic excited state relaxation dynamics of an Fe carbene photosensitizer.

Photoionisation of an atom by X-rays usually removes an inner-shell electron from the atom, leaving behind a perturbed "hollow ion" whose relaxation may take different routes. In light elements, emission of an Auger electron is common. However, the energy and the total number of electrons released from the atom may be modulated by shake-up and shake-off effects. When the inner-shell electron leaves, the outer-shell electrons may find themselves in a state that is not an eigen-state of the atom in its surroundings. The resulting collective excitation is called shake-up. If this process also involves the release of low energy electrons from the outer shell, then the process is called shake-off. It is not clear how significant shake-up and shake-off contributions are to the overall ionisation of biological materials like proteins. In particular, the interaction between the out-going electron and the remaining system depends on the chemical environment of the atom, which can be studied by quantum chemical methods. Here we present calculations on model compounds to represent the most common chemical environments in proteins. The results show that the shake-up and shake-off processes affect about 20% of all emissions from nitrogen, 30% from carbon, 40% from oxygen, and 23% from sulphur. Triple and higher ionisations are rare for carbon, nitrogen and oxygen, but are frequent for sulphur. The findings are relevant to the design of biological experiments at emerging X-ray free-electron lasers., Comment: 14 pages, latex, 1 figure