Related Experiment Video
Updated: Jun 15, 2026

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
Solvent-mediated electron hopping: long-range charge transfer in IBr-(CO2) photodissociation
Leonid Sheps1, Elisa M Miller, Samantha Horvath
1JILA, Department of Chemistry and Biochemistry, University of Colorado at Boulder, Boulder, CO 80309, USA.
Abstract:
Chemical bond breaking involves coupled electronic and nuclear dynamics that can take place on multiple electronic surfaces. Here we report a time-resolved experimental and theoretical investigation of nonadiabatic dynamics during photodissociation of a complex of iodine monobromide anion with carbon dioxide [IBr-(CO2)] on the second excited (A') electronic state. Previous experimental work showed that the dissociation of bare IBr- yields only I- + Br products. However, in IBr-(CO2), time-resolved photoelectron spectroscopy reveals that a subset of the dissociating molecules undergoes an electron transfer from iodine to bromine 350 femtoseconds after the initial excitation. Ab initio calculations and molecular dynamics simulations elucidate the mechanism for this charge hop and highlight the crucial role of the carbon dioxide molecule. The charge transfer between two recoiling atoms, assisted by a single solvent-like molecule, provides a notable limiting case of solvent-driven electron transfer over a distance of 7 angstroms.
Related Concept Videos
Deactivation Processes: Jablonski Diagram
IR Absorption Frequency: Delocalization
In IR spectroscopy,...
Chemical Shift: Internal References and Solvent Effects
The internal reference compound generally used in NMR spectroscopy is tetramethylsilane (TMS). TMS is preferred because it is chemically inert, soluble in NMR solvents, and easily removable. Also, the highly shielded methyl protons in TMS yield an intense...
Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation
Thermal and Photochemical Electrocyclic Reactions: Overview
UV–Vis Spectroscopy: Molecular Electronic Transitions

