Superexchange‐Assisted Through‐Bridge Electron Transfer

Electronic and Dynamical Aspects

Ronnie Kosloff, Mark A Ratner

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

The effects of electronic structure on bridge‐assisted electron transfer are considered. Using static perturbation theory, time‐dependent perturbation theory, and direct time‐dependent dynamics within generalized tight binding models, we examine the role of energy gaps, relative energetics of donor and acceptor orbitals with hole‐type and electron‐type superexchange sites, damping and dephasing, and overall energetics in electron transfer. We find that a generalization of the simple McConnell relationship to nonresonant transfer can in fact be made, but that no simple formula describes all limits; this is important in applications to a number of systems, including photosynthetic reaction centers, in which such superexchange occurs. The dynamical studies indicate some important and unexpected phenomena: these include quantum interferences between different pathways, recurrences and oscillations, and competitive effects of hole‐type and electron‐type superexchange. We suggest that direct dynamical study, as has begun to appear from several laboratories, provides an excellent way to visualize the intermediate state contributions to intramolecular electron transfer processes.

Original languageEnglish
Pages (from-to)45-58
Number of pages14
JournalIsrael Journal of Chemistry
Volume30
Issue number1-2
DOIs
Publication statusPublished - 1990

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Electrons
Photosynthetic Reaction Center Complex Proteins
Electronic structure
Energy gap
Damping

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Superexchange‐Assisted Through‐Bridge Electron Transfer : Electronic and Dynamical Aspects. / Kosloff, Ronnie; Ratner, Mark A.

In: Israel Journal of Chemistry, Vol. 30, No. 1-2, 1990, p. 45-58.

Research output: Contribution to journalArticle

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