Long range electron transfer across π-conjugated systems: role of electron correlations

2005/07/02 by S. Lakshmi, Lakshmi, S., Ayan Datta +3
Chemistry · Engineering · Physics and Astronomy · #FOS: Physical sciences #Mesoscale and Nanoscale Physics (cond-mat.mes-hall) #Photochemistry and Electron Transfer Studies #Soft Condensed Matter (cond-mat.soft) #Spectroscopy and Quantum Chemical Studies #Surface Chemistry and Catalysis #cond-mat.mes-hall #cond-mat.soft

paper · pdf · doi:10.48550/arxiv.cond-mat/0507046

Accepted in Phys. Rev. B

arxiv created 2005/07/02 · openalex publication_date 2005/07/02 · arxiv updated 2009/12/01 · openalex created_date 2016/06/24 · openalex updated_date 2026/07/28

Abstract

We consider a prototype polyene chain: donor-π(bridge)-acceptor. The distance between the donor and the acceptor is varied by increasing the number of bridged atoms and rate of electron transfer, k_et is studied for a series of different donors, D=NH₂, SH, OH, and a fixed acceptor, A=NO₂. We observe a large k_et even at a very large D-A separation of ∼ 45 Å, unexpected from the well-known and standard theories like the Forster theory. Such a long range electron transfer is due to the strong electron-electron interactions in the bridged orbitals that result in deconfinment of electrons in donor orbitals. Calculations at various levels: semi-empirical and many-body exact, have been performed to accurately account for such correlations.

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