Three-centered model of ultrafast photoinduced charge transfer: Continuum dielectric approach
- Department of Physics, Volgograd State University, University Avenue 100, Volgograd 400062 (Russian Federation)
A theoretical description of photoinduced charge transfer involves explicit treating both the optical formation of the nuclear wave packet on the excited free energy surface and its ensuing dynamics. The reaction pathway constitutes two-stage charge transfer between three centers. Manifestations of fractional charge transfer at first stage are explored. An expression for time dependent rate constant of photoinduced charge transfer is found in the framework of the linear dielectric continuum model of the medium. The model involves both the intramolecular vibrational reorganization and the Coulombic interaction of the transferred charge with the medium polarization fluctuations and allows to express the rate in terms of intramolecular reorganization parameters and complex dielectric permittivity. The influence of the vibrational coherent motion in the locally excited state on the charge transfer dynamics has been explored. The dependence of the ultrafast photoinduced charge transfer dynamics on the excitation pulse carrier frequency (spectral effect) has been investigated. The spectral effect has been shown to depend on quantity of the fractional charge.
- OSTI ID:
- 20783248
- Journal Information:
- Journal of Chemical Physics, Vol. 124, Issue 11; Other Information: DOI: 10.1063/1.2178810; (c) 2006 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
Effect of the excitation pulse frequency on the ultrafast photoinduced electron transfer dynamics
Ultrafast heterogeneous electron transfer reactions: Comparative theoretical studies on time- and frequency-domain data