Real-time structural dynamics of the ultrafast solvation process around photo-excited aqueous halides

• Published in: Chemical science (Cambridge) 2024-07, Vol.15 (29), p.11391-1141
• Main Authors: Markmann, Verena, Pan, Jaysree, Hansen, Bianca L, Haubro, Morten L, Nimmrich, Amke, Lenzen, Philipp, Levantino, Matteo, Katayama, Tetsuo, Adachi, Shin-ichi, Gorski-Bilke, Simone, Temps, Friedrich, Dohn, Asmus O, Møller, Klaus B, Nielsen, Martin M, Haldrup, Kristoffer
• Format: Article
• Language: English
• Subjects: Aqueous solutions; Chemical Sciences; Chemistry; Dynamic structural analysis; Dynamics; Electrons; Evolution; Halides; Kemi; Molecular structure; Photoexcitation; Real time; Scattering; Sensitivity analysis; Solvation; Solvents; Water chemistry
• ISSN: 2041-6520; 2041-6539; 2041-6539
• DOI: 10.1039/d4sc01912a

This work investigates and describes the structural dynamics taking place following charge-transfer-to-solvent photo-abstraction of electrons from I − and Br − ions in aqueous solution following single- and 2-photon excitation at 202 nm and 400 nm, respectively. A Time-Resolved X-ray Solution Scattering (TR-XSS) approach with direct sensitivity to the structure of the surrounding solvent as the water molecules adopt a new equilibrium configuration following the electron-abstraction process is utilized to investigate the structural dynamics of solvent shell expansion and restructuring in real-time. The structural sensitivity of the scattering data enables a quantitative evaluation of competing models for the interaction between the nascent neutral species and surrounding water molecules. Taking the I 0 -O distance as the reaction coordinate, we find that the structural reorganization is delayed by 0.1 ps with respect to the photoexcitation and completes on a time scale of 0.5-1 ps. On longer time scales we determine from the evolution of the TR-XSS difference signal that I 0 : e − recombination takes place on two distinct time scales of ∼20 ps and 100 s of picoseconds. These dynamics are well captured by a simple model of diffusive evolution of the initial photo-abstracted electron population where the charge-transfer-to-solvent process gives rise to a broad distribution of electron ejection distances, a significant fraction of which are in the close vicinity of the nascent halogen atoms and recombine on short time scales. Time-resolved X-ray solution scattering with a 1-photon and 2-photon pump qualitatively confirms the ∼0.5 Å increase in the nearest-neighbour halide-oxygen distances of iodide and bromide solvated in water.