Ultrafast kinetics of linkage isomerism in Na 2 [Fe(CN) 5 NO] aqueous solution revealed by time-resolved photoelectron spectroscopy.

The kinetics of ultrafast photoinduced structural changes in linkage isomers is investigated using Na-2[Fe(CN)(5)NO] as a model complex. The buildup of the metastable side-on configuration of the NO ligand, as well as the electronic energy levels of ground, excited, and metastable states, has been revealed by means of timeresolved extreme UV (XUV) photoelectron spectroscopy in aqueous solution, aided by theoretical calculations. Evidence of a short-lived intermediate state in the isomerization process and its nature are discussed, finding that the complete isomerization process occurs in less than 240 fs after photoexcitation. (C) 2017 Author(s).