Ultrafast kinetics of linkage isomerism in Na2[Fe(CN)5NO] aqueous solution revealed by time-resolved photoelectron spectroscopy

Azhr A. Raheem1,2,3, Martin Wilke1,2, Mario Borgwardt1,2, Nicholas Engel1,2, Sergey I. Bokarev4,a), Gilbert Grell4, Saadullah G. Aziz5, Oliver Kühn4, Igor Yu. Kiyan2, Christoph Merschjann1,2,b), and Emad F. Aziz1,2,6,c)

Structural Dynamics 4, 044031 (2017); doi: http://dx.doi.org/10.1063/1.4990567

The kinetics of ultrafast photoinduced structural changes in linkage isomers is investigated using Na2[Fe(CN)5NO] 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 time-resolved 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.

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