Charge and Nuclear Dynamics Induced by Deep Inner-Shell Multiphoton Ionization of CH3I Molecules by Intense X-ray Free-Electron Laser Pulses.

In recent years, free-electron lasers operating in the true X-ray regime have opened up access to the femtosecond-scale dynamics induced by deep inner-shell ionization. We have investigated charge creation and transfer dynamics in the context of molecular Coulomb explosion of a single molecule, exposed to sequential deep inner-shell ionization within an ultrashort (10 fs) X-ray pulse. The target molecule was CH3I, methane sensitized to X-rays by halogenization with a heavy element, iodine. Time-of-flight ion spectroscopy and coincident ion analysis was employed to investigate, via the properties of the atomic fragments, single-molecule charge states of up to +22. Experimental findings have been compared with a parametric model of simultaneous Coulomb explosion and charge transfer in the molecule. The study demonstrates that including realistic charge dynamics is imperative when molecular Coulomb explosion experiments using short-pulse facilities are performed.

Anomalous signal from S atoms in protein crystallographic data from an X-ray free-electron laser.

X-ray free-electron lasers (FELs) enable crystallographic data collection using extremely bright femtosecond pulses from microscopic crystals beyond the limitations of conventional radiation damage. This diffraction-before-destruction approach requires a new crystal for each FEL shot and, since the crystals cannot be rotated during the X-ray pulse, data collection requires averaging over many different crystals and a Monte Carlo integration of the diffraction intensities, making the accurate determination of structure factors challenging. To investigate whether sufficient accuracy can be attained for the measurement of anomalous signal, a large data set was collected from lysozyme microcrystals at the newly established `multi-purpose spectroscopy/imaging instrument' of the SPring-8 Ångstrom Compact Free-Electron Laser (SACLA) at RIKEN Harima. Anomalous difference density maps calculated from these data demonstrate that serial femtosecond crystallography using a free-electron laser is sufficiently accurate to measure even the very weak anomalous signal of naturally occurring S atoms in a protein at a photon energy of 7.3 keV.

Dielectric permittivity of room temperature ionic liquids: a relation to the polar and nonpolar domain structures.

We measured microwave transmission and reflection spectra for typical room temperature ionic liquids, [C(4)min][TFSA], [C(4)min][PF(6)], [C(6)min][PF(6)], and [C(8)min][PF(6)], at frequencies between 40 MHz and 40 GHz in the temperature range up to 100 degrees C. The transmission spectra were analyzed using complex dielectric functions, and the static permittivity epsilon(S) was determined as a function of temperature. Applying the effective medium approximation to epsilon(S), we have estimated that the static permittivity of the polar domain is around 20, and that of the nonpolar domain around 2.5.

Viscoelastic properties of room temperature ionic liquids.

The sound absorption coefficient alpha and sound velocity nu(S) have been measured for 1-alkyl-3-methylimidazolium hexafluorophosphate [Cn mim]PF(6), with n = 8,6,4 and 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C4 mim]TFSI, at the frequencies of 11.3, 34.9, and 57.7 MHz in the temperature range from 293 to 393 K. From the obtained alpha and available viscosity data, [Cn mim]PF(6) with large n proves to be no longer Newtonian liquids at room temperatures. Applying a Maxwell viscoelastic model with the elastic modulus G of a spring and the shear coefficient gamma of a dashpot to the experimental frequency dependence of alpha, one finds that G is insensitive to n, while the relaxation time tau(= gamma/G), which is on the order of nanoseconds, does depend on n.

Decay channel dependence of the photoelectron angular distributions in core-level ionization of Ne dimers.

For K-shell photoionization of neon dimers, we report Ne 1s photoelectron angular distributions for Ne2++Ne+ and Ne++Ne+ channels exhibiting quite different patterns. Noninversion-symmetric patterns of the former obtained by the fast interatomic Coulombic decay of Auger final states show direct evidence of core-hole localization. Dipolar patterns of the latter obtained by the slow radiative decay of the other Auger final states clearly show that the radiative process is slow enough to allow dicationic dimers to rotate many times before fragmentation.

Study of liquid metals as a basis for nanoscience.

There are two ways to proceed with nanoscience: so-called top-down and bottom-up methods. Usually, the former methods are thought of as in the province of physicists and the latter in that of chemists. However, this is not entirely true because the physics of disordered matter, especially liquid metals, is well-developed bottom-up science and it has indeed provided nanoscience with basic ideas and theoretical tools such as ab initio molecular dynamics (MD) simulations. Here we wish to present experimental studies on such phenomena that originate from quantum mechanical properties and subsequently lead to classical non-equilibrium processes: among these are slow dynamics due to metal-nonmetal transitions in liquids, and wetting and dewetting transitions of liquid semiconductors. Since all these phenomena are related to a spatiotemporal range far wider than that treated by the present ab initio MD simulations, it is desirable that new progress in theoretical physics be stimulated, resulting in further developments in nanoscience.