Molecules can efficiently and selectively convert light energy into other degrees of freedom. Disentangling the underlying ultrafast motion of electrons and nuclei of the photoexcited molecule presents a challenge to current spectroscopic approaches. Here we explore the photoexcited dynamics of molecules by an interaction with an ultrafast X-ray pulse creating a highly localized core hole that decays via Auger emission. We discover that the Auger spectrum as a function of photoexcitation-X-ray-probe delay contains valuable information about the nuclear and electronic degrees of freedom from an element-specific point of view. For the nucleobase thymine, the oxygen Auger spectrum shifts towards high kinetic energies, resulting from a particular C-O bond stretch in the pp* photoexcited state. A subsequent shift of the Auger spectrum towards lower kinetic energies displays the electronic relaxation of the initial photoexcited state within 200 fs. Ab-initio simulations reinforce our interpretation and indicate an electronic decay to the np* state.

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Experimental evidence is presented for confinement resonances associated with photoabsorption by a Xe atom in a C60 cage. The giant 4d resonance in photoionization of Xe is predicted to be redistributed into four components due to multipath interference of photoelectron waves reflected by the cage. The measurements were made in the photon energy range 60-150 eV by merging a beam of synchrotron radiation with a mass/charge selected Xe@C₆₀+ ion beam. The phenomenon was observed in the Xe@C(58)(3+) product ion channel. [corrected]

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Mass-selected beams of atomic Ceq+ ions (q = 2, 3, 4), of C82+ and of endohedral Ce@C82+ ions were employed to study photoionization of free and encaged cerium atoms. The Ce 4d inner-shell contributions to single and double ionization of the endohedral Ce@C82+ fullerene have been extracted from the data and compared with expectations based on theory and the experiments with atomic Ce ions. Dramatic reduction and redistribution of the ionization contributions to 4d photoabsorption is observed. More than half of the Ce 4d oscillator strength appears to be diverted to the additional decay channels opened by the fullerene cage surrounding the Ce atom.