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Photooxidation and photoaquation of iron hexacyanide in aqueous solution: A
picosecond X-ray absorption study
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See supplementary material at http://dx.doi.org/10.1063/1.4871751
for the ground state iron K-edge and the UV-visible spectra of both complexes, a transient spectrum over an extended energy range of aqueous ferrous cyanide after 266 nm photoexcitation and the effect of the photolysis yield on the transient spectrum presented in Fig. 2(a)
. [Supplementary Material]
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We present a picosecond Fe K-edge absorption study of photoexcited ferrous and ferric
hexacyanide in water under 355 and 266 nm excitation. Following 355 nm excitation, the
transient spectra for the ferrous and ferric complexes exhibit a red shift of the edge
reflecting an increased electron density at the Fe atom. For the former, an enhanced
pre-edge transition is also observed. These observations are attributed to the aquated
[Fe(CN)5OH2]3− species, based on quantum chemical
calculations which also provide structural parameters. Upon 266 nm excitation of the
ferric complex, a transient reminiscent of the aquated species is observed (appearance of
a pre-edge feature and red
shift of the edge) but it is different from that obtained under 355 nm
excitation. This points to a new reaction channel occurring through an intermediate
state lying between these two excitation energies. Finally, 266 nm excitation of the
ferrous species is dominated by the photooxidation channel with formation of the ferric
complex as main photoproduct. However, we observe an additional minor photoproduct, which
is identical to the 266 nm generated photoproduct of the ferric species, suggesting that
under our experimental conditions, the pump pulse photooxidises the ferrous complex and
re-excites the primary ferric photoproduct.
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