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  Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)5 to Fe(CO)4EtOH.

Kunnus, K., Josefsson, I., Rajkovic, I., Schreck, S., Quevedo, W., Beye, M., et al. (2016). Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)5 to Fe(CO)4EtOH. Structural Dynamics, 3(4): 043204. doi:10.1063/1.4941602.

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 Urheber:
Kunnus, K., Autor
Josefsson, I., Autor
Rajkovic, I.1, Autor           
Schreck, S., Autor
Quevedo, W., Autor
Beye, M., Autor
Weniger, C., Autor
Grübel, S.1, Autor           
Scholz, Mirko1, Autor           
Nordlund, D., Autor
Zhang, W., Autor
Hartsock, R. W., Autor
Gaffney, K. J., Autor
Schlotter, W. F., Autor
Turner, J. J., Autor
Kennedy, B., Autor
Hennies, F., Autor
de Groot, F. M. F., Autor
Techert, S.1, Autor           
Odelius, M., Autor
Wernet, P., AutorFöhlisch, A., Autor mehr..
Affiliations:
1Research Group of Structural Dynamics of (Bio)Chemical Systems, MPI for biophysical chemistry, Max Planck Society, ou_578564              

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 Zusammenfassung: We utilized femtosecond time-resolved resonant inelastic X-ray scattering and ab initio theory to study the transient electronic structure and the photoinduced molecular dynamics of a model metal carbonyl photocatalyst Fe(CO)5 in ethanol solution. We propose mechanistic explanation for the parallel ultrafast intra-molecular spin crossover and ligation of the Fe(CO)4 which are observed following a charge transfer photoexcitation of Fe(CO)5 as reported in our previous study [Wernet et al., Nature 520, 78 (2015)]. We find that branching of the reaction pathway likely happens in the (1)A1 state of Fe(CO)4. A sub-picosecond time constant of the spin crossover from (1)B2 to (3)B2 is rationalized by the proposed (1)B2 → (1)A1 → (3)B2 mechanism. Ultrafast ligation of the (1)B2 Fe(CO)4 state is significantly faster than the spin-forbidden and diffusion limited ligation process occurring from the (3)B2 Fe(CO)4 ground state that has been observed in the previous studies. We propose that the ultrafast ligation occurs via (1)B2 → (1)A1 → (1)A' Fe(CO)4EtOH pathway and the time scale of the (1)A1 Fe(CO)4 state ligation is governed by the solute-solvent collision frequency. Our study emphasizes the importance of understanding the interaction of molecular excited states with the surrounding environment to explain the relaxation pathways of photoexcited metal carbonyls in solution.

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Sprache(n): eng - English
 Datum: 2016-02
 Publikationsstatus: Online veröffentlicht
 Seiten: -
 Ort, Verlag, Ausgabe: -
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 Art der Begutachtung: Expertenbegutachtung
 Identifikatoren: DOI: 10.1063/1.4941602
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Titel: Structural Dynamics
Genre der Quelle: Zeitschrift
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Seiten: 16 Band / Heft: 3 (4) Artikelnummer: 043204 Start- / Endseite: - Identifikator: -