Core excitation triggers nuclear dynamics on the femtosecond time scale. A multiparametric electron/ion coincidence approach has been used to disentangle complex decay processes occurring at short (molecular) or long (atomic) time scales. Methyl chloride has been excited by scanning along the dissociative Cl2p-->sigma* resonance. The detailed chronology of the competing decay processes, leading to either the rearrangement product HCl(+), or an ultrafast dissociation leading to Cl(+), has been investigated. The observed Auger-Doppler shift has been analyzed for various orientations of the electron and fragment ion.

We describe a bent-crystal spectrometer adapted to measure x-ray emission resulting from core-level excitation of gas-phase molecules in the 0.8-8 keV energy range. The spectrometer is based on the Johann principle, and uses a microfocused photon beam to provide high-resolution (resolving power of approximately 7500). A gas cell was designed to hold a high-pressure (300 mbar) sample of gas while maintaining a high vacuum (10(-9) mbar) in the chamber. The cell was designed to optimize the counting rate (2000 cts/s at the maximum of the Cl Kalpha emission line), while minimizing self-absorption. Example of the Kalpha emission lines of CH(3)Cl molecules is presented to illustrate the capabilities of this new instrument.