Creation of deep core holes with very short ($\tau \le 1\mathrm{fs}$) lifetimes triggers a chain of relaxation events leading to extensive nuclear dynamics on a few-femtosecond time scale. Here we demonstrate a general multistep ultrafast dissociation on an example of HCl following Cl $1s\to {\sigma }^{*}$ excitation. Intermediate states with one or multiple holes in the shallower core electron shells are generated in the course of the decay cascades. The repulsive character and large gradients of the potential energy surfaces of these intermediates enable ultrafast fragmentation after the absorption of a hard x-ray photon.

We present here a review of the most significant recent achievements in the field of HAXPES (hard x-ray photoelectron spectroscopy) on isolated atoms and molecules, and related spectroscopies. The possibility of conducting hard x-ray photoexcitation and photoionization experiments under state-of-the art conditions in terms of photon and electron kinetic energy resolution has become available only in the last few years. HAXPES has then produced structural and dynamical information at the level of detail already reached in the VUV and soft-x-ray ranges. The much improved experimental conditions have allowed extending to the hard x-ray range some methods well established in soft x-ray spectroscopies. Investigations of electron and nuclear dynamics in the femtosecond (fs, 10 ⁻¹⁵ s) and even attosecond (as, 10 ⁻¹⁸ s) regime have become feasible. Complex relaxation phenomena following deep-core ionization can now be enlightened in great detail. Other phenomena like e.g. recoil-induced effects are much more important in fast photoelectron emission, which can be induced by hard x-rays. Furthermore, a new kind of ionic states with double core holes can be observed by x-ray single-photon absorption. Future perspectives are also discussed.

Tuning hard x-ray excitation energy along Cl $1s\to {\sigma }^{*}$ resonance in gaseous HCl allows manipulating molecular fragmentation in the course of the induced multistep ultrafast dissociation. The observations are supported by theoretical modeling, which shows a strong interplay between the topology of the potential energy curves, involved in the Auger cascades, and the so-called core-hole clock, which determines the time spent by the system in the very first step. The asymmetric profile of the fragmentation ratios reflects different dynamics of nuclear wave packets dependent on the photon energy.

The ultrafast structural dynamics of water following inner-shell ionization is a crucial issue in high-energy radiation chemistry. We have exposed isolated water molecules to a short x-ray pulse from a free-electron laser and detected momenta of all produced ions in coincidence. By combining experimental results and theoretical modeling, we can image dissociation dynamics of individual molecules in unprecedented detail. We reveal significant molecular structural dynamics in ${\mathrm{H}}_2{\mathrm{O}}^{2+}$, such as asymmetric deformation and bond-angle opening, leading to two-body or three-body fragmentation on a timescale of a few femtoseconds. We thus reconstruct several snapshots of structural dynamics at different time intervals, which highlight dynamical patterns that are relevant as initiating steps of subsequent radiation-damage processes.

We study vibrationally-resolved resonant Auger (RAS) spectra of ammonia recorded in coincidence with the NH₂ ⁺ fragment, which is produced in the course of dissociation either in the core-excited 1s⁻¹4a¹ ₁ intermediate state or the first spectator 3a⁻²4a¹ ₁ final state. Correlation of the NH₂ ⁺ ion flight times with electron kinetic energies allows directly observing the Auger-Doppler dispersion for each vibrational state of the fragment. The median distribution of the kinetic energy release E_KER, derived from the coincidence data, shows three distinct branches as a function of Auger electron kinetic energy E_e: E_e + 1.75E_KER = const for the molecular band; E_KER = const for the fragment band; and E_e + E_KER = const for the region preceding the fragment band. The deviation of the molecular band dispersion from E_e + E_KER = const is attributed to the redistribution of the available energy to the dissociation energy and excitation of the internal degrees of freedom in the molecular fragment. We found that for each vibrational line the dispersive behavior of E_KERvs. E_e is very sensitive to the instrumental uncertainty in the determination of E_KER causing the competition between the Raman (E_KER + E_e = const) and Auger (E_e = const) dispersions: increase in the broadening of the finite kinetic energy release resolution leads to a change of the dispersion from the Raman to the Auger one.