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  • Schnorr, Kirsten, et al. (författare)
  • Tracing the 267 nm-Induced Radical Formation in Dimethyl Disulfide Using Time-Resolved X-ray Absorption Spectroscopy
  • 2019
  • Ingår i: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 10:6, s. 1382-1387
  • Tidskriftsartikel (refereegranskat)abstract
    • Disulfide bonds are pivotal for the structure, function, and stability of proteins, and understanding ultraviolet (UV)-induced S–S bond cleavage is highly relevant for elucidating the fundamental mechanisms underlying protein photochemistry. Here, the near-UV photodecomposition mechanisms in gas-phase dimethyl disulfide, a prototype system with a S–S bond, are probed by ultrafast transient X-ray absorption spectroscopy. The evolving electronic structure during and after the dissociation is simultaneously monitored at the sulfur L1,2,3-edges and the carbon K-edge with 100 fs (FWHM) temporal resolution using the broadband soft X-ray spectrum from a femtosecond high-order harmonics light source. Dissociation products are identified with the help of ADC and RASPT2 electronic-structure calculations. Rapid dissociation into two CH3S radicals within 120 ± 30 fs is identified as the major relaxation pathway after excitation with 267 nm radiation. Additionally, a 30 ± 10% contribution from asymmetric CH3S2 + CH3 dissociation is indicated by the appearance of CH3 radicals, which is, however, at least partly the result of multiphoton excitation.
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