A broadband ultrafast investigation of sodide charge transfer to solvent (CTTS) dynamics

• Applicant: Professor Dr. Thomas Elsässer
• Co-Applicant: Professor Sanford Ruhman, Ph.D.
• Subject Area: Physical Chemistry of Molecules, Liquids and Interfaces, Biophysical Chemistry
• Term: from 2006 to 2010
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 29181571

• Final Report Year: 2009

Final Report Abstract

We have, for the first lime, followed the dynamics of photoionization of anions in solution, otherwise known as charge transfer to solvent (CTTS) with high time resolution and simultaneously probing both fragments. We find that for sodide ions in tetrahydrofurane (THF) this process lakes place much more rapidly than previously thought based on theoretical models, and other experimental studies. We have also uncovered two new fundamental reactive stages of this process. One relates to the solvation and relaxation of the ejected electrons which shows up as a continuous and dynamic blue shifting ofthe electron's absorption. The other is a direct recombination process which takes place without loss of binding between the fragments for a minority of the irradiated ions with low energy photons. We are convinced that these results are relevant to other CTTS processes in electrolyte solutions, and are therefore of general importance to the whole field of electron transfer in condensed phases.

Publications

• Na photolysis in THF: CTTS studied from the donors perspective in <10 fsec detail, J. Chem. Phys. 129, 044502 (2008)
  O. Shoshanim, S. Ruhman