A unified electron transfer model for the different precursors and excited states of the hydrated electron
Date
2001
Authors
Kee, T.
Son, D.
Kambhampati, P.
Barbara, P.
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Journal article
Citation
The Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory, 2001; 105(37):8434-8439
Statement of Responsibility
Tak W. Kee, Dong Hee Son, Patanjali Kambhampati, and Paul F. Barbara
Conference Name
Abstract
Femtosecond spectroscopy measurements are reported on the electron transfer, ET, reactions of the precursor states of the hydrated electron in the multiphoton ionization of water and the single-photon ionization of Fe(CN)6[sup]4- in aqueous solutions. The ET reaction corresponds to an electron scavenging by various electron acceptors, such as Cd[sup]2+. Using the data reported herein, and previously published data on the scavenging kinetics of other electron precursors (e.g., from radiolysis) and optically excited states of the hydrated electron, it was shown that the rate constant of ET varies inversely with the volume of specific form of the hydrated electron. These data strongly support a unified model for the electron-transfer kinetics of many forms of delocalized electrons with localized electron acceptors in which ET rates are assumed to be proportional to the average electron density of the specific hydrated electron excited state or precursor.
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Copyright © 2001 American Chemical Society