Building a molecular-level picture of the ultrafast dynamics of
the charge-transfer-to-solvent (CTTS) reaction of sodide (Na�)
I. B. Martini, E. R. Barthel, and B. J. Schwartz
Department of Chemistry and Biochemistry, University
of California, Los Angeles, Los Angeles, CA 90095-1569, USA
Abstract: Charge-transfer-to-solvent (CTTS) reactions represent
the simplest possible electron-transfer reaction. One of the reasons
that such reactions have become the subject of recent interest is that
transfer of a CTTS electron from an atomic anion to the solvent involves
only electronic degrees of freedom, so that all the dynamics involved
in the reaction are those of the solvent. Thus, CTTS reactions provide
an outstanding spectroscopic window on the dynamics of the solvent during
electron transfer. In this paper, we will review our recent work studying
the CTTS reaction of the sodium anion, (Na– or sodide)
in a series of ether solvents. By comparing the results of ultrafast
spectroscopic pump/probe experiments and mixed quantum/classical molecular
dynamics simulations, we work to build a molecular-level picture of
how solvent motions control the dynamics of CTTS, including the distance
to which the electron is ejected and the rates of both the forward and
back electron-transfer reactions.
*Plenary lecture presented at the 28th International
Conference on Solution Chemistry, Debrecen, Hungary, 23-28 August 2003.
Other presentations are published in this issue, pp.
1809-1919.
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