Photoinduced electron transfer and geminate recombination in solution

Journal Article · Thu Feb 18 04:00:00 EST 1993 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100109a021· OSTI ID:6043413

Song, L; Swallen, S F; Dorfman, R C; Weidemaier, K; Fayer, M D ^[1]

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1. Stanford Univ., CA (United States)

Intermolecular electron transfer and geminate recombination are explored experimentally in both solid and liquid solutions using the same donor-acceptor pair. The solvents were chosen to have similar chemical and dielectric properties, but vastly different viscosities. Systems of an electron donor, rubrene, and varying concentrations of an electron acceptor, duroquinone, were studied. The solvents used were diethyl sebacate (liquid) and sucrose octaacetate (solid). Forward electron transfer was studied using time-resolved and steady-state fluorescence measurements for a variety of acceptor concentrations. Electron back-transfer (geminate recombination) was measured using pump-probe experiments. The data were analyzed using a theoretical treatment that takes into account diffusion of the donor and acceptors, a distance-dependent (exponential) transfer rate, Coulomb interactions between the ions generated by the forward transfer, and donor-acceptor and acceptor-acceptor excluded volumes. The forward transfer data, in both the solid and liquid solutions, are in very good agreement with calculations. Virtually identical forward transfer parameters are obtained from the solid and liquid samples. The back-transfer parameters obtained from the measurements on solid solution are able to reproduce the liquid solution's back-transfer data, but only when the high-frequency dielectric constant is used. The use of this value for the dielectric constant is discussed. 48 refs., 10 figs.

• DOE Contract Number: FG03-84ER13251
• OSTI ID: 6043413
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 97:7; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400500* -- Photochemistry
AROMATICS
BENZOQUINONES
CHEMISTRY
DIFFUSION
DISPERSIONS
ELECTRON TRANSFER
ESTERS
FLUORESCENCE
LUMINESCENCE
MIXTURES
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PHOTOCHEMISTRY
QUINONES
SOLID SOLUTIONS
SOLUTIONS
SOLVENTS