Communication: Direct evidence for sequential dissociation of gas-phase $\mathrm{Fe(CO)_5}$ via a singlet pathway upon excitation at 266 nm

Wernet, Philippe; Leitner, T.; Beye, Martin; Kunnus, K.; Düsterer, S.; Föhlisch, A.; Odelius, M.; Schreck, S.; Mazza, T.; Miedema, Piter; Radcliffe, P.; Josefsson, I.; Schröder, Henning; Meyer, Michael

doi:10.1063/1.4984774

Journal Article

PUBDB-2017-04558

Communication: Direct evidence for sequential dissociation of gas-phase $\mathrm{Fe(CO)_5}$ via a singlet pathway upon excitation at 266 nm

Wernet, P. (Corresponding author)Extern* ; Leitner, T.Extern* ; Josefsson, I. ; Mazza, T.XFEL.EU* ; Miedema, P.DESY* ; Schröder, H. ; Beye, M.DESY* ; Kunnus, K.Extern* ; Schreck, S.Extern* ; Radcliffe, P. ; Düsterer, S.DESY* ; Meyer, M.XFEL.EU* ; Odelius, M. (Corresponding author) ; Föhlisch, A.Extern*

2017
American Institute of Physics Melville, NY

The journal of chemical physics 146(21), 211103 (2017) [10.1063/1.4984774]

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Please use a persistent id in citations: doi:10.1063/1.4984774 doi:10.3204/PUBDB-2017-04558

Abstract: We prove the hitherto hypothesized sequential dissociation of Fe(CO)$_5$ in the gas phase upon photoexcitation at 266 nm via a singlet pathway with time-resolved valence and core-level photoelectron spectroscopy with an x-ray free-electron laser. Valence photoelectron spectra are used to identify free CO molecules and to determine the time constants of stepwise dissociation to Fe(CO)$_4$ within the temporal resolution of the experiment and further to Fe(CO)$_3$ within 3 ps. Fe 3p core-level photoelectron spectra directly reflect the singlet spin state of the Fe center in Fe(CO)$_5$, Fe(CO)$_4$, and Fe(CO)$_3$ showing that the dissociation exclusively occurs along a singlet pathway without triplet-state contribution. Our results are important for assessing intra- and intermolecular relaxation processes in the photodissociation dynamics of the prototypical Fe(CO)$_5$ complex in the gas phase and in solution, and they establish time-resolved core-level photoelectron spectroscopy as a powerful tool for determining the multiplicity of transition metals in photochemical reactions of coordination complexes.

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