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We show that X-ray pulses resonant with selected core transitions can manipulate electron transfer (ET) in molecules with ultrafast and atomic selectivity. We present possible protocols for coherently controlling ET dynamics in donor-bridge-acceptor (DBA) systems by stimulated X-ray resonant Raman processes involving various transitions between the D, B, and A sites. Simulations presented for a Ru(II)-Co(III) model complex demonstrate how the shapes, phases and amplitudes of the X-ray pulses can be optimized to create charge on demand at selected atoms, by opening up otherwise blocked ET pathways.

Attosecond transient absorption is an ultrafast technique that has opened the possibility to study electron dynamics in condensed matter systems at its natural timescale. The extension to the x-ray regime permits one to use this powerful technique in combination with the characteristic element specificity of x-ray spectroscopy. At these timescales, the coherent effects of the electron transport are essential and have a relevant signature on the absorption spectrum. Typically, the complex light-driven dynamics requires a theoretical modeling for shedding light on the time-dependent changes in the spectrum. Here we construct a semiconductor Bloch equation model for resolving the light-induced and core-electron dynamics simultaneously, which enables to easily disentangle the interband and intraband contributions. By using the Bloch model, we demonstrate a universal feature on attosecond x-ray transient absorption spectra that emerges from the light-induced coherent intraband dynamics. This feature is linked to previous studies of light-induced Fano resonances in atomic systems.

Abstract: Photoexcited states of a pyrazolate bridged PtPt dimer and a supramolecular RuCo complex with bipyridine-type ligands were studied using the pump-and-probe X-ray absorption spectroscopy method. The local structure refinement based on the fitting of XANES difference spectra has been performed. The theoretical analysis included the full multiple scattering calculations and the multidimensional interpolation of spectra as a function of structural parameters. The influence of possible correlations between the fraction of molecules in the photoexcited state and structural parameters is discussed. [Copyright &y& Elsevier]

Abstract: We report on a joint experimental–theoretical effort to shed light on the dynamics of rare gas (Ar) nanoclusters irradiated by short and intense laser pulses. The experiments employ a streak camera coupled to a conical crystal to yield energy- and time-resolved X-ray spectra, in the keV range on picosecond scale. These spectra display ultrafast subpicosecond ionization dynamics, leading to highly charged states such as Ar16+, and indicate that the duration of the energetic X-rays is less than the experimental 1.3ps temporal resolution. The theoretical calculations rely on the well-known nanoplasma model, which has been improved to represent the collisional ionization processes that are of importance in nanoplasma dynamics. Allowance is made for high-order ionization transitions involving intermediate excited states. The simulations indicate significant populations of excited states of highly charged ions, in agreement with the experimental findings. Further, detailed collisional-radiative calculations indicate that the duration of the X-ray bursts is less than 100fs. [Copyright &y& Elsevier]