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

Autor:	Markmann V; Technical University of Denmark Anker Engelunds Vej 1 2800 Lyngby Denmark vmark@dtu.dk., Pan J; Technical University of Denmark Anker Engelunds Vej 1 2800 Lyngby Denmark vmark@dtu.dk., Hansen BL; Technical University of Denmark Anker Engelunds Vej 1 2800 Lyngby Denmark vmark@dtu.dk., Haubro ML; Technical University of Denmark Anker Engelunds Vej 1 2800 Lyngby Denmark vmark@dtu.dk., Nimmrich A; Technical University of Denmark Anker Engelunds Vej 1 2800 Lyngby Denmark vmark@dtu.dk.; Department of Chemistry and Molecular Biology, University of Gothenburg Gothenburg Sweden., Lenzen P; Technical University of Denmark Anker Engelunds Vej 1 2800 Lyngby Denmark vmark@dtu.dk., Levantino M; European Synchrotron Radiation Facility CS40220 Grenoble 38043 Cedex 9 France., Katayama T; Japan Synchrotron Radiation Research Institute Kouto 1-1-1, Sayo Hyogo 679-5198 Japan.; RIKEN SPring-8 Center 1-1-1 Kouto, Sayo Hyogo 679-5148 Japan., Adachi SI; Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK) 1-1 Oho, Tsukuba Ibaraki 305-0801 Japan.; Department of Materials Structure Science, School of High Energy Accelerator Science 1-1 Oho, Tsukuba Ibaraki 305-0801 Japan., Gorski-Bilke S; Christian-Albrechts-University Kiel Olshausenstr. 40 24098 Kiel Germany., Temps F; Christian-Albrechts-University Kiel Olshausenstr. 40 24098 Kiel Germany., Dohn AO; Technical University of Denmark Anker Engelunds Vej 1 2800 Lyngby Denmark vmark@dtu.dk.; Science Institute, University of Iceland 107 Reykjavík Iceland., Møller KB; Technical University of Denmark Anker Engelunds Vej 1 2800 Lyngby Denmark vmark@dtu.dk., Nielsen MM; Technical University of Denmark Anker Engelunds Vej 1 2800 Lyngby Denmark vmark@dtu.dk., Haldrup K; Technical University of Denmark Anker Engelunds Vej 1 2800 Lyngby Denmark vmark@dtu.dk.
Jazyk:	angličtina
Zdroj:	Chemical science [Chem Sci] 2024 Jun 12; Vol. 15 (29), pp. 11391-11401. Date of Electronic Publication: 2024 Jun 12 (Print Publication: 2024).
DOI:	10.1039/d4sc01912a
Abstrakt:	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. Competing Interests: There are no conflicts to declare. (This journal is © The Royal Society of Chemistry.)
Databáze:	MEDLINE
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