Ultrafast Photovoltaic Response in Ferroelectric Nanolayers

We show that light drives large-amplitude structural changes in thin films of the prototypical ferroelectric PbTiO[subscript 3] via direct coupling to its intrinsic photovoltaic response. Using time-resolved x-ray scattering to visualize atomic displacements on femtosecond time scales, photoinduced changes in the unit-cell tetragonality are observed. These are driven by the motion of photogenerated free charges within the ferroelectric and can be simply explained by a model including both shift and screening currents, associated with the displacement of electrons first antiparallel to and then parallel to the ferroelectric polarization direction.United States. Dept. of Energy (contract DE-FG02-07ER46431)United States. Office of Naval Research (grant N00014-06-1- 0459

Femtosecond X-ray Absorption Spectroscopy at a Hard X-ray Free Electron Laser: Application to Spin Crossover Dynamics

X-ray free electron lasers (XFELs) deliver short (<100 fs) and intense (1012 photons) pulses of hard X-rays, making them excellent sources for time-resolved studies. Here we show that, despite the inherent instabilities of current (SASE based) XFELs, they can be used for measuring high-quality X-ray absorption data and we report femtosecond time-resolved X-ray absorption near-edge spectroscopy (XANES) measurements of a spin-crossover system, iron(II) tris(2,2′-bipyridine) in water. The data indicate that the low-spin to high-spin transition can be modeled by single-exponential kinetics convoluted with the overall time resolution. The resulting time constant is 160 fs