Unified expression for the rate constant of the bridged electron transfer derived by renormalization

Journal Article · Wed Oct 07 00:00:00 EDT 2009 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3223280· OSTI ID:21559785

Saito, Keisuke; Sumi, Hitoshi ^[1]

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1. Institute of Materials Science, University of Tsukuba, Tsukuba 305-8573 (Japan)

Electron transfer (ET) from a donor to an acceptor through an energetically close intermediary state on a midway molecule is a process found often in natural and artificial solar-energy capturing systems such as photosynthesis. This process has often been thought of in terms of opposing 'superexchange' and 'sequential or hopping' mechanisms, and the recent theory of Sumi and Kakitani (SK) [J. Phys. Chem. B 105, 9603 (2001)] has shown an interpolation between these mechanisms. In their theory, however, dynamics governing the most interesting intermediary region between them has artificially been introduced by phenomenologies. The dynamics is played by decoherence among electronic states, their decay, and thermalization of phonons in the medium. The present work clarifies the dynamics on a microscopic basis by means of renormalization in electronic coupling among the states, and gives a complete unified expression of the rate constant of the ET. It merges to that given by the SK theory in the semiclassical approximation for phonons interacting with an electron transferred.

• OSTI ID: 21559785
• Journal Information: Journal of Chemical Physics, Vol. 131, Issue 13; Other Information: DOI: 10.1063/1.3223280; (c) 2009 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
CHARGE-EXCHANGE REACTIONS
ELECTRON TRANSFER
INTERPOLATION
MOLECULES
PHONONS
PHOTOSYNTHESIS
REACTION KINETICS
RENORMALIZATION
SEMICLASSICAL APPROXIMATION
SOLAR ENERGY
THERMALIZATION
APPROXIMATIONS
CALCULATION METHODS
CHEMICAL REACTIONS
ENERGY
ENERGY SOURCES
KINETICS
MATHEMATICAL SOLUTIONS
NUCLEAR REACTIONS
NUMERICAL SOLUTION
PHOTOCHEMICAL REACTIONS
QUASI PARTICLES
RENEWABLE ENERGY SOURCES
SLOWING-DOWN
SYNTHESIS