Acetylene's scission visualized by selfie: Can molecules take pictures of themselves? That is more or less the principle underlying laser-induced electron diffraction (LIED): A laser field strips an electron from a molecule and then sends it back to report on the structure of the remaining ion. Wolter et al. applied this technique to acetylene to track the cleavage of its C–H bond after double ionization (see the Perspective by Ruan). They imaged the full structure of the molecule and also distinguished more rapid dissociative dynamics when it was oriented parallel rather than perpendicular to the LIED field. Science , this issue p. 308 ; see also p. 283

Despite their broad implications for phenomena such as molecular bonding or chemical reactions, our knowledge of multi-electron dynamics is limited and their theoretical modelling remains a most difficult task. From the experimental side, it is highly desirable to study the dynamical evolution and interaction of the electrons over the relevant timescales, which extend into the attosecond regime. Here we use near-single-cycle laser pulses with well-defined electric field evolution to confine the double ionization of argon atoms to a single laser cycle. The measured two-electron momentum spectra, which substantially differ from spectra recorded in all previous experiments using longer pulses, allow us to trace the correlated emission of the two electrons on sub-femtosecond timescales. The experimental results, which are discussed in terms of a semiclassical model, provide strong constraints for the development of theories and lead us to revise common assumptions about the mechanism that governs double ionization.

Strong-field physics is currently experiencing a shift towards the use of mid-IR driving wavelengths. This is because they permit conducting experiments unambiguously in the quasistatic regime and enable exploiting the effects related to ponderomotive scaling of electron recollisions. Initial measurements taken in the mid-IR immediately led to a deeper understanding of photoionization and allowed a discrimination among different theoretical models. Ponderomotive scaling of rescattering has enabled new avenues towards time-resolved probing of molecular structure. Essential for this paradigm shift was the convergence of two experimental tools: (1) intense mid-IR sources that can create high-energy photons and electrons while operating within the quasistatic regime and (2) detection systems that can detect the generated high-energy particles and image the entire momentum space of the interaction in full coincidence. Here, we present a unique combination of these two essential ingredients, namely, a 160-kHz mid-IR source and a reaction microscope detection system, to present an experimental methodology that provides an unprecedented three-dimensional view of strong-field interactions. The system is capable of generating and detecting electron energies that span a 6 order of magnitude dynamic range. We demonstrate the versatility of the system by investigating electron recollisions, the core process that drives strong-field phenomena, at both low (meV) and high (hundreds of eV) energies. The low-energy region is used to investigate recently discovered low-energy structures, while the high-energy electrons are used to probe atomic structure via laser-induced electron diffraction. Moreover, we present, for the first time, the correlated momentum distribution of electrons from nonsequential double ionization driven by mid-IR pulses.

Laser-induced electron diffraction is an evolving tabletop method that aims to image ultrafast structural changes in gas-phase polyatomic molecules with sub-Ångström spatial and femtosecond temporal resolutions. Here we demonstrate the retrieval of multiple bond lengths from a polyatomic molecule by simultaneously measuring the C–C and C–H bond lengths in aligned acetylene. Our approach takes the method beyond the hitherto achieved imaging of simple diatomic molecules and is based on the combination of a 160 kHz mid-infrared few-cycle laser source with full three-dimensional electron–ion coincidence detection. Our technique provides an accessible and robust route towards imaging ultrafast processes in complex gas-phase molecules with atto- to femto-second temporal resolution.

The lifetime of interatomic Coulombic decay (ICD) [L. S. Cederbaum et al., Phys. Rev. Lett. 79, 4778 (1997)] in ${\mathrm{Ne}}_2$ is determined via an extreme ultraviolet pump-probe experiment at the Free-Electron Laser in Hamburg. The pump pulse creates a $2s$ inner-shell vacancy in one of the two Ne atoms, whereupon the ionized dimer undergoes ICD resulting in a repulsive ${\mathrm{Ne}}^{+}(2p^{-1})-{\mathrm{Ne}}^{+}(2p^{-1})$ state, which is probed with a second pulse, removing a further electron. The yield of coincident ${\mathrm{Ne}}^{+}-{\mathrm{Ne}}^{2+}$ pairs is recorded as a function of the pump-probe delay, allowing us to deduce the ICD lifetime of the ${\mathrm{Ne}}_2^{+}(2s^{-1})$ state to be $(150\pm 50)\mathrm{fs}$, in agreement with quantum calculations.