Double core hole spectroscopy with synchrotron radiation

In the last five years, a strong experimental and theoretical activity has been dedicated to the study of inner-shell double photoionization. Almost simultaneously, between 2009 and 2011, different experiments were performed using two different light sources: well established third generation synchrotron light sources that exist for more than two decades and recently developed x-ray free electron lasers (X-FEL) that provide brightness of about 10 orders of magnitude higher. The high photon flux of X-FEL has made possible the successive absorption of many x-ray photons by inner-shell electrons in femtosecond timescale. The possibility to create multiple inner-shell vacancies with this new X-FEL light source has resuscitated "prophetic" 25 years old calculations by Cederbaum et al. [1,2] concerning double K-shell ionization that could be of great interest when conventional Electron Spectroscopy for Chemical Analysis (ESCA) finds some limitations. As a feedback, this has stimulated new theoretical developments. On the other hand, it was considered practically out of reach to observe such states with conventional third generation synchrotron light sources due to the very weak probability to eject two inner-shell electrons by a single photon when the dominant process, that could mask everything else, is single inner-shell ionization. However, due to the development of very efficient detection techniques, it was also possible to perform spectroscopy of double core-hole states with excellent accuracy using third generation synchrotron sources. In this paper we give an outlook on the basis of recently published results, of the complementarity of these light sources for double core-hole spectroscopy. Some new developments and results are also presented with a prospective of what could be done in the future with the technical breakthrough that will be necessary to improve our further understanding of chemical analysis.