Understanding molecular femtosecond dynamics under intense X-ray exposure is critical to progress in biomolecular imaging and matter under extreme conditions. Imaging viruses and proteins at an atomic spatial scale and on the time scale of atomic motion requires rigorous, quantitative understanding of dynamical effects of intense X-ray exposure. Here we present an experimental and theoretical study of C 60 molecules interacting with intense X-ray pulses from a free-electron laser, revealing the influence of processes not previously reported. Our work illustrates the successful use of classical mechanics to describe all moving particles in C 60 , an approach that scales well to larger systems, for example, biomolecules. Comparisons of the model with experimental data on C 60 ion fragmentation show excellent agreement under a variety of laser conditions. The results indicate that this modelling is applicable for X-ray interactions with any extended system, even at higher X-ray dose rates expected with future light sources.

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The low density matter end-station at the new seeded free electron laser FERMI@Elettra is a versatile instrument for the study of atoms, molecules and clusters by means of electron and ion spectroscopies. Beams of atoms, molecules and helium droplets as well as clusters of atoms, molecules and metals can be produced by three different pulsed valves. The atomic and molecular beams may be seeded, and the clusters and droplets may be pure, or doped with other atoms and molecules. The electrons and ions produced by the ionization and fragmentation of the samples by the intense light of FERMI can be analysed by the available spectrometers, to give mass spectra and energy as well as angular distributions of charged particles. The design of the detector allows simultaneous detection of electrons and ions using velocity map imaging and time-of-flight techniques respectively. The instruments have a high energy/mass resolution and large solid-angle collection efficiency. We describe the current status of the apparatus and illustrate the potential for future experiments.

Relative (e,2e) triply differential cross sections (TDCS) are measured for the ionization of the helium atom and the hydrogen molecule in coplanar asymmetric geometry at a scattered electron energy of 500 eV and ejected electron energies of 205, 74 and 37 eV. The He experimental results are found to be in very good agreement with convergent close-coupling calculations (CCC). The H2 experimental results are compared with two state-of-the-art available theoretical models for treating differential electron impact ionization of molecules. Both models yield an overall good agreement with experiments, except for some intensity deviations in the recoil region. Similar (e,2e) works were recently published on H2 with contrasted conclusions to the hypothesis that the two H nuclei could give rise to an interference pattern in the TDCS structure. Murray (2005 J. Phys. B: At. Mol. Opt. Phys. 38 1999) found no evidence for such an effect, whereas Milne-Brownlie et al (2006 Phys. Rev. Lett. 96 233201) reported its indirect observation. In this work, based on a direct comparison between experimental results for He and H2, we observe an oscillatory pattern due to these interference effects, and for the first time the destructive or constructive character of the interference is observed, depending on the de Broglie wavelength of the ejected electron wave. The experimental finding is in good agreement with the theoretical prediction by Stia et al (2003 J. Phys. B: At. Mol. Opt. Phys. 36 L257).

The Coulomb explosion of the hydrogen molecule, after absorption of a 76 eV photon, has been studied by momentum imaging the two electrons and the two protons. Absolute fully differential cross sections of high statistical quality are obtained. A subset of the overall data, namely, equal electron-energy sharing, is used to investigate the effects of molecular orientation on the photoelectron angular distribution. Departures from the first-order helium-like model are evident in detection geometries where electron-electron correlation is "frozen."

Ultrafast extreme ultraviolet and X-ray free-electron lasers are set to revolutionize many domains such as bio-photonics and materials science, in a manner similar to optical lasers over the past two decades. Although their number will grow steadily over the coming decade, their complete characterization remains an elusive goal. This represents a significant barrier to their wider adoption and hence to the full realization of their potential in modern photon sciences. Although a great deal of progress has been made on temporal characterization and wavefront measurements at ultrahigh extreme ultraviolet and X-ray intensities, only few, if any progress on accurately measuring other key parameters such as the state of polarization has emerged. Here we show that by combining ultra-short extreme ultraviolet free electron laser pulses from FERMI with near-infrared laser pulses, we can accurately measure the polarization state of a free electron laser beam in an elegant, non-invasive and straightforward manner using circular dichroism.

The inner shell excitation of pyrimidine and some halogenated pyrimidines near the C and N K-edges has been investigated experimentally by near edge x-ray absorption fine structure spectroscopy and theoretically by density functional theory calculations. The selected targets, 5-Br-pyrimidine, 2-Br-pyrimidine, 2-Cl-pyrimidine, and 5-Br-2-Cl-pyrimidine, allow the effects of the functionalization of the pyrimidine ring to be studied either as a function of different halogen atoms bound to the same molecular site or as a function of the same halogen atom bound to different molecular sites. The results show that the individual characteristics of the different spectra of the substituted pyrimidines can be rationalized in terms of variations in electronic and geometrical structures of the molecule depending on the localization and the electronegativity of the substituent.

A combined experimental and theoretical approach has been used to disentangle the fundamental mechanisms of the fragmentation of the three isomers of nitroimidazole induced by vacuum ultra-violet (VUV) radiation, namely, 4-, 5-, and 2-nitroimidazole. The results of mass spectrometry as well as photoelectron–photoion coincidence spectroscopy display striking differences in the radiation-induced decomposition of the different nitroimidazole radical cations. Based on density functional theory (DFT) calculations, a model is proposed which fully explains such differences, and reveals the subtle fragmentation mechanisms leading to the release of neutral species like NO, CO, and HCN. Such species have a profound impact in biological media and may play a fundamental role in radiosensitising mechanisms during radiotherapy.