Resolving structures of transition metal complex reaction intermediates with femtosecond EXAFS

Femtosecond-resolved Extended X-ray Absorption Fine Structure (EXAFS) measurements of solvated transition metal complexes are successfully implemented at the X-ray Free Electron Laser LCLS. Benchmark experiments on [Fe(terpy)(2)](2+) in solution show a signal-to-noise ratio on the order of 500, comparable to typical 100 ps-resolution synchrotron measurements. In the few femtoseconds after photoexcitation, we observe the EXAFS fingerprints of a short-lived (similar to 100 fs) intermediate as well as those of a vibrationally hot long-lived (similar to ns) excited state.