6533b820fe1ef96bd12791f0

RESEARCH PRODUCT

Real-time observation of the charge transfer to solvent dynamics

Andrea CannizzoAndrea CannizzoOlivier BrämMajed CherguiFabrizio MessinaFabrizio Messina

subject

electron transfer ultrafast fluorescence charge-transfer-to-solvent solvation homogeneity.Physics::Biological PhysicsMultidisciplinaryMaterials scienceAqueous solutionSettore FIS/01 - Fisica SperimentaleGeneral Physics and AstronomyHalideCharge (physics)General ChemistryElectron620 EngineeringGeneral Biochemistry Genetics and Molecular BiologyCondensed Matter::Soft Condensed MatterSolventElectron transferChemical physicsScientific methodPhysics::Chemical PhysicsSolvent effectsSettore CHIM/02 - Chimica Fisica

description

Intermolecular 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 (similar to 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.

yearjournalcountryeditionlanguage
2013-07-01Nature Communications
https://doi.org/10.1038/ncomms3119