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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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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-002A-506E-F Version Permalink: http://hdl.handle.net/11858/00-001M-0000-002C-8146-D
Genre: Journal Article

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

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 Abstract: 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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Language(s): eng - English
 Dates: 2016-02
 Publication Status: Published online
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 Rev. Method: Peer
 Identifiers: DOI: 10.1063/1.4941602
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Title: Structural Dynamics
Source Genre: Journal
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Pages: 16 Volume / Issue: 3 (4) Sequence Number: 043204 Start / End Page: - Identifier: -