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- Borne, Kurtis D., et al.
(författare)
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Ultrafast electronic relaxation pathways of the molecular photoswitch quadricyclane
- 2024
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Ingår i: NATURE CHEMISTRY. - 1755-4330 .- 1755-4349. ; 16, s. 499-505
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Tidskriftsartikel (refereegranskat)abstract
- The light-induced ultrafast switching between molecular isomers norbornadiene and quadricyclane can reversibly store and release a substantial amount of chemical energy. Prior work observed signatures of ultrafast molecular dynamics in both isomers upon ultraviolet excitation but could not follow the electronic relaxation all the way back to the ground state experimentally. Here we study the electronic relaxation of quadricyclane after exciting in the ultraviolet (201 nanometres) using time-resolved gas-phase extreme ultraviolet photoelectron spectroscopy combined with non-adiabatic molecular dynamics simulations. We identify two competing pathways by which electronically excited quadricyclane molecules relax to the electronic ground state. The fast pathway (<100 femtoseconds) is distinguished by effective coupling to valence electronic states, while the slow pathway involves initial motions across Rydberg states and takes several hundred femtoseconds. Both pathways facilitate interconversion between the two isomers, albeit on different timescales, and we predict that the branching ratio of norbornadiene/quadricyclane products immediately after returning to the electronic ground state is approximately 3:2.
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| 3. |
- Sedaghati, Elyar, et al.
(författare)
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A spectral survey of WASP-19b with ESPRESSO
- 2021
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Ingår i: Monthly Notices of the Royal Astronomical Society. - : Oxford University Press (OUP). - 0035-8711 .- 1365-2966. ; 505:1, s. 435-458
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Forskningsöversikt (refereegranskat)abstract
- High-resolution precision spectroscopy provides a multitude of robust techniques for probing exoplanetary atmospheres. We present multiple VLT/ESPRESSO transit observations of the hot-Jupiter exoplanet WASP-19b with previously published but disputed atmospheric features from lowresolution studies. Through spectral synthesis and modelling of the Rossiter-McLaughlin (RM) effect we calculate stellar, orbital and physical parameters for the system. From narrow-band spectroscopy we do not detect any of HI, FeI, MgI, CaI, NaI, and KI neutral species, placing upper limits on their line contrasts. Through cross-correlation analyses with atmospheric models, we do not detect Fe I and place a 3σ upper limit of log (XFe/X⊙) ≈ -1.83 ± 0.11 on its mass fraction, from injection and retrieval. We show the inability to detect the presence of H2O for known abundances, owing to lack of strong absorption bands, as well as relatively low S/N ratio. We detect a barely significant peak (3.02±0.15 σ) in the cross-correlation map for TiO, consistent with the sub-solar abundance previously reported. This is merely a hint for the presence of TiO and does not constitute a confirmation. However, we do confirm the presence of previously observed enhanced scattering towards blue wavelengths, through chromatic RM measurements, pointing to a hazy atmosphere. We finally present a reanalysis of low-resolution transmission spectra of this exoplanet, concluding that unocculted starspots alone cannot explain previously detected features. Our reanalysis of the FORS2 spectra of WASP-19b finds a ~100× sub-solar TiO abundance, precisely constrained to log XTiO ≈ -7.52 ± 0.38, consistent with the TiO hint from ESPRESSO. We present plausible paths to reconciliation with other seemingly contradicting results.
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