Endre søk
RefereraExporteraLink to record
Permanent link

Direct link
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Annet format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annet språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf
Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)(5) to Fe(CO)(4)EtOH
Stockholms universitet, Naturvetenskapliga fakulteten, Fysikum.ORCID-id: 0000-0002-8621-4282
Vise andre og tillknytning
Rekke forfattare: 222016 (engelsk)Inngår i: Structural Dynamics, ISSN 2329-7778, Vol. 3, nr 4, artikkel-id 043204Artikkel i tidsskrift (Fagfellevurdert) 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.

sted, utgiver, år, opplag, sider
2016. Vol. 3, nr 4, artikkel-id 043204
HSV kategori
Identifikatorer
URN: urn:nbn:se:su:diva-135065DOI: 10.1063/1.4941602ISI: 000383880700006PubMedID: 26958587OAI: oai:DiVA.org:su-135065DiVA, id: diva2:1061863
Konferanse
Femto 12 The Hamburg Conference on Femtochemistry, Hamburg, Germany, July 12-17, 2015
Tilgjengelig fra: 2017-01-03 Laget: 2016-10-31 Sist oppdatert: 2019-12-17bibliografisk kontrollert

Open Access i DiVA

Fulltekst mangler i DiVA

Andre lenker

Forlagets fulltekstPubMed

Søk i DiVA

Av forfatter/redaktør
Josefsson, IdaOdelius, Michael
Av organisasjonen

Søk utenfor DiVA

GoogleGoogle Scholar

doi
pubmed
urn-nbn

Altmetric

doi
pubmed
urn-nbn
Totalt: 7 treff
RefereraExporteraLink to record
Permanent link

Direct link
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Annet format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annet språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf