Watching Excited State Dynamics with Optical and X-ray Probes : The Excited State Dynamics of Aquocobalamin and Hydroxocobalamin
Femtosecond time-resolved X-ray absorption (XANES) at the Co K-edge, X-ray emission (XES) in the Co Kβ and valence-to-core regions, and broadband UV-vis transient absorption are combined to probe the femtosecond to picosecond sequential atomic and electronic dynamics following photoexcitation of two vitamin B12 compounds, hydroxocobalamin and aquocobalamin. Polarized XANES difference spectra allow identification of sequential structural evolution involving first the equatorial and then the axial ligands, with the latter showing rapid coherent bond elongation to the outer turning point of the excited state potential followed by recoil to a relaxed excited state structure. Time-resolved XES, especially in the valence-to-core region, along with polarized optical transient absorption suggests that the recoil results in the formation of a metal-centered excited state with a lifetime of 2-5 ps. This combination of methods provides a uniquely powerful tool to probe the electronic and structural dynamics of photoactive transition-metal complexes and will be applicable to a wide variety of systems.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2023 |
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| Erschienen: |
2023 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:145 |
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| Enthalten in: |
Journal of the American Chemical Society - 145(2023), 25 vom: 28. Juni, Seite 14070-14086 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Sension, Roseanne J [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Completed 28.06.2023 Date Revised 28.06.2023 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/jacs.3c04099 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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NLM358288959 |
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| 100 | 1 | |a Sension, Roseanne J |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Watching Excited State Dynamics with Optical and X-ray Probes |b The Excited State Dynamics of Aquocobalamin and Hydroxocobalamin |
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| 500 | |a Date Revised 28.06.2023 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a Femtosecond time-resolved X-ray absorption (XANES) at the Co K-edge, X-ray emission (XES) in the Co Kβ and valence-to-core regions, and broadband UV-vis transient absorption are combined to probe the femtosecond to picosecond sequential atomic and electronic dynamics following photoexcitation of two vitamin B12 compounds, hydroxocobalamin and aquocobalamin. Polarized XANES difference spectra allow identification of sequential structural evolution involving first the equatorial and then the axial ligands, with the latter showing rapid coherent bond elongation to the outer turning point of the excited state potential followed by recoil to a relaxed excited state structure. Time-resolved XES, especially in the valence-to-core region, along with polarized optical transient absorption suggests that the recoil results in the formation of a metal-centered excited state with a lifetime of 2-5 ps. This combination of methods provides a uniquely powerful tool to probe the electronic and structural dynamics of photoactive transition-metal complexes and will be applicable to a wide variety of systems | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a McClain, Taylor P |e verfasserin |4 aut | |
| 700 | 1 | |a Lamb, Ryan M |e verfasserin |4 aut | |
| 700 | 1 | |a Alonso-Mori, Roberto |e verfasserin |4 aut | |
| 700 | 1 | |a Lima, Frederico Alves |e verfasserin |4 aut | |
| 700 | 1 | |a Ardana-Lamas, Fernando |e verfasserin |4 aut | |
| 700 | 1 | |a Biednov, Mykola |e verfasserin |4 aut | |
| 700 | 1 | |a Chollet, Matthieu |e verfasserin |4 aut | |
| 700 | 1 | |a Chung, Taewon |e verfasserin |4 aut | |
| 700 | 1 | |a Deb, Aniruddha |e verfasserin |4 aut | |
| 700 | 1 | |a Dewan, Paul A |c Jr |e verfasserin |4 aut | |
| 700 | 1 | |a Gee, Leland B |e verfasserin |4 aut | |
| 700 | 1 | |a Huang Ze En, Joel |e verfasserin |4 aut | |
| 700 | 1 | |a Jiang, Yifeng |e verfasserin |4 aut | |
| 700 | 1 | |a Khakhulin, Dmitry |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Jianhao |e verfasserin |4 aut | |
| 700 | 1 | |a Michocki, Lindsay B |e verfasserin |4 aut | |
| 700 | 1 | |a Miller, Nicholas A |e verfasserin |4 aut | |
| 700 | 1 | |a Otte, Florian |e verfasserin |4 aut | |
| 700 | 1 | |a Uemura, Yohei |e verfasserin |4 aut | |
| 700 | 1 | |a van Driel, Tim B |e verfasserin |4 aut | |
| 700 | 1 | |a Penner-Hahn, James E |e verfasserin |4 aut | |
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