Transmission spectroscopy of CF$_4$ molecules in intense x-ray fields

TL;DR

This study uses high-intensity x-ray transmission spectroscopy with XFEL pulses to observe ultrafast molecular fragmentation and transient species in CF$_4$, revealing nonlinear multiphoton effects and dissociation dynamics at femtosecond timescales.

Contribution

It introduces a novel experimental approach combining XFEL transmission spectroscopy with gas-phase molecules to directly observe transient fragments and nonlinear effects during ultrafast molecular dissociation.

Findings

Observation of transient neutral and ionic fluorine fragments within femtoseconds.

Identification of an isosbestic point indicating transition between neutral and charged molecules.

Demonstration of nonlinear multiphoton absorption effects in CF$_4$ under intense x-ray fields.

Abstract

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 multi-photon absorption processes. In this work, intense x-ray free-electron laser (XFEL) pulses at the European XFEL (EuXFEL) 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 intra-pulse observation of transient fragments, including neutral atoms, by their characteristic absorption lines in the transmitted broad-band 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 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.