Time dependence of donor--acceptor electron transfer and back transfer in solid solution

Journal Article · Sun Jan 01 00:00:00 EST 1989 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.456509· OSTI ID:6596644

Lin, Y; Dorfman, R C; Fayer, M D

Electron transfer from an optically excited donor to randomly distributed acceptors followed by electron back transfer is treated theoretically for donors and acceptors in a rigid solution. The forward electron transfer process is described in terms of the excited state population probabilityP/sub ex/(t) of the donor molecules, while the electron back transfer from the radical anion to the radical cation is characterized by P/sub ct/(t), the donor cation state population probability. Exact expressions for the ensemble averages and are derived. Numerical calulations are presented for the cation probabilities, the average cation--anion separation distance , and the average cation existence time , using parameters which characterize the forward and back transfer distance dependent rates. Relationships among , and the intermolecular interaction parameters provide detailed insights into the distance and time dependence of the flow of electron probability in an ensemble of donors and acceptors. The theoretical expressions can be used to calculate experimental observables. In particular, picosecond transient grating experiments are analyzed, and it is shown that by combining grating experiments (or other ground state recovery experiments) with fluorescence experiments it is possible to obtain the intermolecular interaction parameters for both forward and back transfer and a detailed description of the dynamics.

• Research Organization: Department of Chemistry, Stanford University, Stanford, California 94305
• OSTI ID: 6596644
• Journal Information: J. Chem. Phys.; (United States), Vol. 90:1
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
SOLID SOLUTIONS
ELECTRON TRANSFER
PHOTOCHEMICAL REACTIONS
ENERGY-LEVEL DENSITY
EXCITATION
ION PAIRS
RECOMBINATION
TIME DEPENDENCE
CHEMICAL REACTIONS
DISPERSIONS
ENERGY-LEVEL TRANSITIONS
MIXTURES
SOLUTIONS
400500* - Photochemistry
400201 - Chemical & Physicochemical Properties