X-ray free electron lasers (XFELs) providing ultrashort intense pulses of X-rays have proven to be excellent tools to investigate the dynamics of radiation-induced dissociation and charge redistribution in molecules and nanoparticles. Coincidence techniques, in particular multi-ion time-of-flight (TOF) coincident experiments, can provide detailed information on the photoabsorption, charge generation, and Coulomb explosion events. Here we review several such recent experiments performed at the SPring-8 Angstrom Compact free electron LAser (SACLA) facility in Japan, with iodomethane, diiodomethane, and 5-iodouracil as targets. We demonstrate how to utilize the momentum-resolving capabilities of the ion TOF spectrometers to resolve and filter the coincidence data and extract various information essential in understanding the time evolution of the processes induced by the XFEL pulses.

The increasing availability of X-ray free-electron lasers (XFELs) has catalyzed the development of single-object structural determination and of structural dynamics tracking in real-time. Disentangling the molecular-level reactions triggered by the interaction with an XFEL pulse is a fundamental step towards developing such applications. Here we report real-time observations of XFEL-induced electronic decay via short-lived transient electronic states in the diiodomethane molecule, using a femtosecond near-infrared probe laser. We determine the lifetimes of the transient states populated during the XFEL-induced Auger cascades and find that multiply charged iodine ions are issued from short-lived (∼20 fs) transient states, whereas the singly charged ones originate from significantly longer-lived states (∼100 fs). We identify the mechanisms behind these different time scales: contrary to the short-lived transient states which relax by molecular Auger decay, the long-lived ones decay by an interatomic Coulombic decay between two iodine atoms, during the molecular fragmentation.

We carried out time-of-flight mass spectrometry for neon clusters that were exposed to intense free electron laser pulses with the wavelength of 62 nm, which induce optical transition from the ground state (2s2 2p6) to an excited state (2s2 2p5 nl ) in the Ne atoms. In contrast to Ne+ ions produced by two-photon absorption from isolated Ne atoms, the Ne+ ion yield from Ne clusters shows a linear dependence on the laser intensity (I). We discuss the ionization mechanisms which give the linear behaviour with respect to I and expected features in the electron emission spectrum.

The Coulomb explosion of $K$ -shell ionized krypton clusters with an average size $⟨N⟩$ of 160 has been studied by electron-multiple-ion-coincidence measurements in which the time-of-flight (TOF) of ions was measured by using a position sensitive detector. The authors have sorted the TOF spectra by the number of coincidence ion signals, $N_{\text{coin}}$ , and found that singly charged fragment ions such as ${\mathrm{Kr}}^{+}$ , ${\mathrm{Kr}}_2^{+}$ , and ${\mathrm{Kr}}_3^{+}$ are dominant for $N_{\text{coin}}⩾2$ , and that multiply charged ions are detected mainly for $N_{\text{coin}}=1$ . The $N_{\text{coin}}$ dependence of the peak widths in the TOF spectra reveals that the average momentum of the ${\mathrm{Kr}}^{+}$ ions increases with $N_{\text{coin}}$ , while those of ${\mathrm{Kr}}_2^{+}$ and ${\mathrm{Kr}}_3^{+}$ decrease. These results have been more directly confirmed by the momentum imaging measurements. The authors propose that the heavier ions are produced in the central part of clusters where the Coulomb interactions from the surrounding ions are more effectively canceled out due to the higher symmetry.

Carbon 1s photoelectron angular distributions of an iodomethane molecule were measured relative to the recoil-frame determined by the momentum correlation between I⁺ and ${\mathrm{C}\mathrm{H}}_3^{+}$ at photoelectron energies of 3, 6.1, and 12 eV. The energy dependent behavior of the recoil-frame photoelectron angular distributions is reproduced reasonably well by the time-dependent density functional theory with B-spline methods. We discuss potential applications of the fully differential photoelectron angular distribution measurements in the molecular frame to three-dimensional molecular structural determinations identifying the directions and lengths of the bonds.