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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)(4)EtOH
Stockholm University, Faculty of Science, Department of Physics.
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Number of Authors: 22
2016 (English)In: Structural Dynamics, ISSN 2329-7778, Vol. 3, no 4, 043204Article in journal (Refereed) Published
Abstract [en]

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)A(1) state of Fe(CO)(4). A sub-picosecond time constant of the spin crossover from B-1(2) to B-3(2) is rationalized by the proposed B-1(2) -> (1)A(1) -> B-3(2) mechanism. Ultrafast ligation of the B-1(2) Fe(CO)(4) state is significantly faster than the spin-forbidden and diffusion limited ligation process occurring from the B-3(2) Fe(CO)(4) ground state that has been observed in the previous studies. We propose that the ultrafast ligation occurs via B-1(2) -> (1)A(1) -> (1)A'Fe(CO)(4)EtOH pathway and the time scale of the (1)A(1) 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.

Place, publisher, year, edition, pages
2016. Vol. 3, no 4, 043204
National Category
Chemical Sciences Physical Sciences
URN: urn:nbn:se:su:diva-135065DOI: 10.1063/1.4941602ISI: 000383880700006PubMedID: 26958587OAI: diva2:1061863
Femto 12 The Hamburg Conference on Femtochemistry, Hamburg, Germany, July 12-17, 2015
Available from: 2017-01-03 Created: 2016-10-31 Last updated: 2017-01-03Bibliographically approved

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