We measure molecular vibrations with femtometer precision via resonance energy shifts using time-resolved x-ray absorption spectroscopy. For a demonstration, a Raman process excites the $A_{1g}$ mode in gas-phase ${\mathrm{SF}}_6$ molecules with an amplitude of approximately $50\mathrm{fm}$, which is probed by a time-delayed soft-x-ray pulse at the sulfur $L_{2,3}$ edge. Mapping the extremely small measured energy shifts to internuclear distances requires an understanding of the electronic contributions provided by a many-body ab initio simulation. Our study establishes core-level spectroscopy as a precision tool for time-dependent molecular-structure metrology.

Electronic interactions play a fundamental role in atoms, molecular structure and reactivity. We introduce a general concept to control the effective electronic exchange interaction with intense laser fields via coupling to excited states. As an experimental proof of principle, we study the ${\mathrm{SF}}_6$ molecule using a combination of soft x-ray and infrared (IR) laser pulses. Increasing the IR intensity increases the effective exchange energy of the core hole with the excited electron by 50%, as observed by a characteristic spin-orbit branching ratio change. This work demonstrates altering electronic interactions by targeting many-particle quantum properties.

The electronic and nuclear dynamics inside molecules are essential for chemical reactions, where different pathways typically unfold on ultrafast timescales. Extreme ultraviolet (XUV) light pulses generated by free-electron lasers (FELs) allow atomic-site and electronic-state selectivity, triggering specific molecular dynamics while providing femtosecond resolution. Yet, time-resolved experiments are either blind to neutral fragments or limited by the spectral bandwidth of FEL pulses. Here, we combine a broadband XUV probe pulse from high-order harmonic generation with an FEL pump pulse to observe dissociation pathways leading to fragments in different quantum states. We temporally resolve the dissociation of a specific O ₂ ⁺ state into two competing channels by measuring the resonances of ionic and neutral fragments. This scheme can be applied to investigate convoluted dynamics in larger molecules relevant to diverse science fields.

We report on numerical results revealing line-shape asymmetry changes of electronic transitions in atoms near-resonantly driven by intense extreme-ultraviolet (XUV) electric fields by monitoring their transient absorption spectrum after transmission through a moderately dense atomic medium. Our numerical model utilizes ultrashort broadband XUV laser pulses varied in their intensity (10¹⁴–10¹⁵ W/cm²) and detuning nearly out of resonance for a quantitative evaluation of the absorption line-shape asymmetry. It will be shown how transient energy shifts of the bound electronic states can be linked to these asymmetry changes in the case of an ultrashort XUV driving pulse temporally shorter than the lifetime of the resonant excitation, and how the asymmetry can be controlled by the near-resonant detuning of the XUV pulse. In the case of a two-level system, the numerical model is compared to an analytical calculation, which helps to uncover the underlying mechanism for the detuning- and intensity-induced line-shape modification and links it to the generalized Rabi frequency. To further apply the numerical model to recent experimental results of the near-resonant dressing of the 2s2p doubly excited state in helium by an ultrashort XUV free-electron laser pulse we extend the two-level model with an ionization continuum, thereby enabling the description of transmission-type (Fraunhofer-like) transient absorption of a strongly laser-coupled autoionizing state.

The nonlinear interaction of x rays with matter is at the heart of understanding and controlling ultrafast molecular dynamics from an atom-specific viewpoint, providing new scientific and analytical opportunities to explore the structure and dynamics of small quantum systems. At increasingly high x-ray intensity, the sensitivity of ultrashort x-ray pulses to specific electronic states and emerging short-lived transient intermediates is of particular relevance for our understanding of fundamental multiphoton absorption processes. In this work, intense x-ray free-electron laser (XFEL) pulses at the European XFEL are combined with a gas cell and grating spectrometer for a high-intensity transmission spectroscopy study of multiphoton-induced ultrafast molecular fragmentation dynamics in CF 4 . This approach unlocks the direct intrapulse observation of transient fragments, including neutral atoms, by their characteristic absorption lines in the transmitted broadband x-ray spectrum. The dynamics with and without initially producing fluorine K -shell holes are studied by tuning the central photon energy. The absorption spectra are measured at different FEL intensities to observe nonlinear effects. Transient isolated fluorine atoms and ions are spectroscopically recorded within the ultrashort pulse duration of a few tens of femtoseconds. An isosbestic point that signifies the correlated transition between intact neutral CF 4 molecules and charged atomic fragments is observed near the fluorine K edge. The dissociation dynamics and the multiphoton absorption-induced dynamics encoded in the spectra are theoretically interpreted. Overall, this study demonstrates the potential of high-intensity x-ray transmission spectroscopy to study ultrafast molecular dynamics with sensitivity to specific intermediate species and their electronic structure.

We simulate ultrafast electronic transitions in an atom and corresponding absorption line changes with a numerical, few-level model, similar to previous work. In addition, a convolutional neural network (CNN) is employed for the first time to predict electronic state populations based on the simulated modifications of the absorption lines. We utilize a two-level and four-level system, as well as a variety of laser-pulse peak intensities and detunings, to account for different common scenarios of light–matter interaction. As a first step towards the use of CNNs for experimental absorption data in the future, we apply two different noise levels to the simulated input absorption data.