ntermolecular electron-transfer reactions have a crucial role in biology, solution chemistry and electrochemistry. The first step of such reactions is the expulsion of the electron to the solvent, whose mechanism is determined by the structure and dynamical response of the latter. Here we visualize the electron transfer to water using ultrafast fluorescence spectroscopy with polychromatic detection from the ultraviolet to the visible region, upon photo-excitation of the so-called charge transfer to solvent states of aqueous iodide. The initial emission is short lived (~60 fs) and it relaxes to a broad distribution of lower-energy charge transfer to solvent states upon rearrangement of the solvent cage. This distribution reflects the inhomogeneous character of the solvent cage around iodide. Electron ejection occurs from the relaxed charge transfer to solvent states with lifetimes of 100–400 fs that increase with decreasing emission energy.

Messina, F., Braem, O., Cannizzo, A., Chergui, M. (2013). Real-time observation of the charge transfer to solvent dynamics. NATURE COMMUNICATIONS, 4(4), 2119 [10.1038/ncomms3119].

Real-time observation of the charge transfer to solvent dynamics

MESSINA, Fabrizio;
2013-01-01

Abstract

ntermolecular electron-transfer reactions have a crucial role in biology, solution chemistry and electrochemistry. The first step of such reactions is the expulsion of the electron to the solvent, whose mechanism is determined by the structure and dynamical response of the latter. Here we visualize the electron transfer to water using ultrafast fluorescence spectroscopy with polychromatic detection from the ultraviolet to the visible region, upon photo-excitation of the so-called charge transfer to solvent states of aqueous iodide. The initial emission is short lived (~60 fs) and it relaxes to a broad distribution of lower-energy charge transfer to solvent states upon rearrangement of the solvent cage. This distribution reflects the inhomogeneous character of the solvent cage around iodide. Electron ejection occurs from the relaxed charge transfer to solvent states with lifetimes of 100–400 fs that increase with decreasing emission energy.
2013
Settore FIS/01 - Fisica Sperimentale
Settore CHIM/02 - Chimica Fisica
Messina, F., Braem, O., Cannizzo, A., Chergui, M. (2013). Real-time observation of the charge transfer to solvent dynamics. NATURE COMMUNICATIONS, 4(4), 2119 [10.1038/ncomms3119].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10447/80772
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