Journal
SCIENCE
Volume 328, Issue 5975, Pages 220-224Publisher
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.1184616
Keywords
-
Categories
Funding
- NSF
- Air Force Office of Scientific Research
- Office of Naval Research
- Graduate School at The Ohio State University
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0848242] Funding Source: National Science Foundation
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0809391] Funding Source: National Science Foundation
Ask authors/readers for more resources
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.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available