Publication Date:
2010-03-06
Description:
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.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Sheps, Leonid -- Miller, Elisa M -- Horvath, Samantha -- Thompson, Matthew A -- Parson, Robert -- McCoy, Anne B -- Lineberger, W Carl -- New York, N.Y. -- Science. 2010 Apr 9;328(5975):220-4. doi: 10.1126/science.1184616. Epub 2010 Mar 4.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉JILA, Department of Chemistry and Biochemistry, University of Colorado at Boulder, Boulder, CO 80309, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/20203015" target="_blank"〉PubMed〈/a〉
Print ISSN:
0036-8075
Electronic ISSN:
1095-9203
Topics:
Biology
,
Chemistry and Pharmacology
,
Computer Science
,
Medicine
,
Natural Sciences in General
,
Physics
