Rapid proton migration is a key process in hydrocarbon photochemistry. Charge migration and subsequent proton motion can mitigate radiation damage when heavier atoms absorb X-rays. If rapid enough, this can improve the fidelity of diffract-before-destroy measurements of biomolecular structure at X-ray-free electron lasers. Here we study X-ray-initiated isomerization of acetylene, a model for proton dynamics in hydrocarbons. Our time-resolved measurements capture the transient motion of protons following X-ray ionization of carbon K-shell electrons. We Coulomb-explode the molecule with a second precisely delayed X-ray pulse and then record all the fragment momenta. These snapshots at different delays are combined into a 'molecular movie' of the evolving molecule, which shows substantial proton redistribution within the first 12 fs. We conclude that significant proton motion occurs on a timescale comparable to the Auger relaxation that refills the K-shell vacancy.

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Free-electron lasers providing ultra-short high-brightness pulses of X-ray radiation have great potential for a wide impact on science, and are a critical element for unravelling the structural dynamics of matter. To fully harness this potential, we must accurately know the X-ray properties: intensity, spectrum and temporal profile. Owing to the inherent fluctuations in free-electron lasers, this mandates a full characterization of the properties for each and every pulse. While diagnostics of these properties exist, they are often invasive and many cannot operate at a high-repetition rate. Here, we present a technique for circumventing this limitation. Employing a machine learning strategy, we can accurately predict X-ray properties for every shot using only parameters that are easily recorded at high-repetition rate, by training a model on a small set of fully diagnosed pulses. This opens the door to fully realizing the promise of next-generation high-repetition rate X-ray lasers.

Nitrogen molecules in ambient air exposed to an intense near-infrared femtosecond laser pulse give rise to cavity-free superradiant emission at 391.4 and 427.8 nm. An unexpected pulse duration-dependent cyclic variation of the superradiance intensity is observed when the central wavelength of the femtosecond pump laser pulse is finely tuned between 780 and 820 nm, and no signal occurs at the resonant wavelength of 782.8 nm (2ω_{782.8  nm}=ω_{391.4  nm}). On the basis of a semiclassical recollision model, we show that an interference of dipolar moments of excited ions created by electron recollisions explains this behavior.

We present the first measurement of the vectorial response of strongly dressed helium atoms probed by an attosecond pulse train (APT) polarised either parallel or perpendicular to the dressing field polarisation. The transient absorption is probed as a function of delay between the APT and the linearly polarised 800 nm field of peak intensity´-1.3 10 W cm 14 2 . The APT spans the photon energy range 16-42 eV, covering the first ionisation energy of helium (24.59 eV). With parallel polarised dressing and probing fields, we observe modulations with periods of one half and one quarter of the dressing field period. When the polarisation of the dressing field is altered from parallel to perpendicular with respect to the APT polarisation we observe a large suppression in the modulation depth of the above ionisation threshold absorption. In addition to this we present the intensity dependence of the harmonic modulation depth as a function of delay between the dressing and probe fields, with dressing field peak intensities ranging from 2×10 12 to 2×10 14 -W cm 2 . We compare our experimental results with a full-dimensional solution of the single-atom time-dependent (TD) Schrödinger equation obtained using the recently developed abinitio TD B-spline ADC method and find good qualitative agreement for the above threshold harmonics.