Phonon-lifetimes in demixing systems.

The dynamics of silver-alkali halide mixed single crystals (Ag(x)Na(1-x)Br, x = 0.23, 0.35, 0.40 and 0.70) were studied by inelastic neutron scattering during the process of spinodal decomposition. Using the thermal three-axes spectrometer PUMA as well as the time-of-flight spectrometer IN5, the time evolution of phonons was observed in time-resolved, stroboscopic measurements. Complementary to the study of long wavelength acoustic phonons, as studied previously, we extended these investigations to Brillouin-zone boundary modes that are particularly sensitive to variations of the local structure. Starting from the homogeneous mixed phase the behaviour of these modes during demixing is observed in real-time. A simple dynamical model based on local structure variants helps to interpret the results. It is shown that the phonon lifetimes vary strongly during the phase separation and increase drastically during the coarsening process. Up to a critical size of precipitates of about 10 nm, zone-boundary modes are found to be strongly damped, while beyond the line widths are reduced to the experimental resolution. This finding leads to the conclusion that the typical mean free path of these modes is of the order of 10 nm, which corresponds to 20 unit cells.

Aspects of the photodimerization mechanism of 2,4-dichlorocinnamic acid studied by kinetic photocrystallography.

Photoinduced structural variations in single crystals of 2,4-dichloro-trans-cinnamic acid (C9H6Cl2O2, DiClCA) have been investigated using X-ray diffraction (photocrystallography) and optical spectroscopic methods. During UV irradiation, which initiates the irreversible dimerization reaction, a loss of the long-range order of the reactant single crystal was found, i.e., that the dimerization is a heterogeneous one. This unexpected result emphasizes the still-existing problem of predicting changes or of remaining periodicity during chemical reactions in the solid state. On the basis of the experimental results, we propose a qualitative kinetic reaction scheme for DiClCA heterogeneous dimerization reaction.

Femtosecond time-resolved powder diffraction experiments using hard X-ray free-electron lasers.

In the next decade the scientific community expects a strong impact in physics, chemistry, biology, material research and life sciences by the availability of high-brilliance X-ray radiation from free-electron laser (FEL) sources. In particular, in the field of ultrafast science these new sources will allow new types of experiments, enabling new phenomena to be discovered. Whereas today ultrafast X-ray diffraction experiments are strongly restricted by the limited X-ray flux of current sources of sub-picosecond X-ray pulses, FELs will provide short pulses of typically 10(12) photons with a duration of the order of 100 fs and monochromaticity of 10(-3). Here, the feasibility of time-resolved single-shot powder diffraction experiments using these intense pulses, and the requirements of these experiments, are discussed. The detector count rates are estimated for diffraction from a model compound in a wide q-regime under the special consideration of high resolving power. In the case of LCLS radiation parameters, single-shot experiments will be feasible although high-resolution powder diffraction will require a reduction of the intrinsic FEL radiation bandwidth.

Experimental requirements for light-induced reactions in powders investigated by time-resolved X-ray diffraction.

A general outline of how to perform a light-excited time-resolved diffraction experiment by applying the optical pump/X-ray probe technique is given. Owing to the difference in penetration depths between the optical light (laser) pump and the X-ray probe, only specific or specially designed crystalline systems can be investigated, so special requirements have to be fulfilled concerning the sample and its compartments. A summary of the experimental conditions of optical pump/X-ray probe experiments is presented, emphasizing why the use of powder diffraction is a useful and necessary X-ray technique for this kind of experiment. The possibilities and bottlenecks of time-resolved X-ray diffraction on the picosecond time scale will be demonstrated in the powder diffraction studies of N,N-dimethylaminobenzonitrile and N,N-diisopropylaminobenzonitrile, where the photo-induced structural changes of these molecular organic systems have been studied as a function of time.