Title: Femtosecond response of polyatomic molecules to ultra-intense hard X-rays

We report x-ray free-electron lasers enable the investigation of the structure and dynamics of diverse systems, including atoms, molecules, nanocrystals and single bioparticles, under extreme conditions. Many imaging applications that target biological systems and complex materials use hard X-ray pulses with extremely high peak intensities (exceeding 10 ²⁰ watts per square centimetre). However, fundamental investigations have focused mainly on the individual response of atoms and small molecules using soft X-rays with much lower intensities. Studies with intense X-ray pulses have shown that irradiated atoms reach a very high degree of ionization, owing to multiphoton absorption, which in a heteronuclear molecularmore » system occurs predominantly locally on a heavy atom (provided that the absorption cross-section of the heavy atom is considerably larger than those of its neighbours) and is followed by efficient redistribution of the induced charge. In serial femtosecond crystallography of biological objects—an application of X-ray free-electron lasers that greatly enhances our ability to determine protein structure—the ionization of heavy atoms increases the local radiation damage that is seen in the diffraction patterns of these objects and has been suggested as a way of phasing the diffraction data. On the basis of experiments using either soft or less-intense hard X-rays, it is thought that the induced charge and associated radiation damage of atoms in polyatomic molecules can be inferred from the charge that is induced in an isolated atom under otherwise comparable irradiation conditions. Here we show that the femtosecond response of small polyatomic molecules that contain one heavy atom to ultra-intense (with intensities approaching 10 ²⁰ watts per square centimetre), hard (with photon energies of 8.3 kiloelectronvolts) X-ray pulses is qualitatively different: our experimental and modelling results establish that, under these conditions, the ionization of a molecule is considerably enhanced compared to that of an individual heavy atom with the same absorption cross-section. This enhancement is driven by ultrafast charge transfer within the molecule, which refills the core holes that are created in the heavy atom, providing further targets for inner-shell ionization and resulting in the emission of more than 50 electrons during the X-ray pulse. Fnally, our results demonstrate that efficient modelling of X-ray-driven processes in complex systems at ultrahigh intensities is feasible.« less

An era of exploring the interactions of high-intensity, hard X-rays with matter has begun with the start-up of a hard-X-ray free-electron laser, the Linac Coherent Light Source (LCLS). Understanding how electrons in matter respond to ultra-intense X-ray radiation is essential for all applications. Here we reveal the nature of the electronic response in a free atom to unprecedented high-intensity, short-wavelength, high-fluence radiation (respectively 10{sup 18} W cm{sup -2}, 1.5-0.6 nm, {approx}10{sup 5} X-ray photons per {angstrom}{sup 2}). At this fluence, the neon target inevitably changes during the course of a single femtosecond-duration X-ray pulse - by sequentially ejecting electrons -more » to produce fully-stripped neon through absorption of six photons. Rapid photoejection of inner-shell electrons produces 'hollow' atoms and an intensity-induced X-ray transparency. Such transparency, due to the presence of inner-shell vacancies, can be induced in all atomic, molecular and condensed matter systems at high intensity. Quantitative comparison with theory allows us to extract LCLS fluence and pulse duration. Our successful modelling of X-ray/atom interactions using a straightforward rate equation approach augurs favourably for extension to complex systems.« less

We review our work on the photo-induced insulator-metaltransition in the strongly correlated, spin-Peierls compound VO2. Ourpump-probe experiments exploit the full spectral range of modernfemtosecond science, combining time-resolved mid-IR and visibletechniques with ultrafast soft x-ray absorption and hard x-raydiffraction. We also report on the switching behavior of VO2nanoparticles embedded in Silica or in optical fibers, a new route toincorporate complex, photo-active materials into technologically viableenvironments.

We consider the new mechanism of X-ray generation by clusters under irradiation by femtosecond laser pulses, the so-called collective photorecombination. We develop the theory of the photo-recombination of electrons that pass from atomic clusters at the outer ionization to the ground level of a homogeneously charged cluster. Such a cluster is considered to be a quantum potential well. The dipole approximation is inapplicable for this process. We conclude that X-ray photons in collective photorecombination on a charged cluster as a whole have an energy that is much larger than that for photorecombination on separate atomic ions inside the cluster. Formore » a typical cluster of 2.25 x 10{sup 6} electrons, with a radius R = 300 A, and a number density of plasma electrons n{sub e} = 2 x 10{sup 22} cm{sup -3}, we find that at a 5% outer ionization of this cluster, the energy of hard X-ray photons is 7.2 keV.« less