Length-dependence of electron transfer coupling matrix in polyene wires: Ab initio molecular orbital theory study

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The electron transfer (ET) properties of π-electron conjugated quasione-dimensional molecular wires, consisting of polyene, [> CAC < ] n (n = 1-11), including β-carotene, is investigated using ab initio molecular orbital theory within Koopmans theorem (KT) approach. The ET coupling matrix element, V DA, for 1,3-transbutadiene molecule calculated with the KT approach shows excellent agreement with the corresponding results obtained with two-state model. The calculated values of V DA for the polyene oligomers exhibit exponential decrease in magnitude with increasing length of the wire. However, the decay curve exhibits three different regimes. The magnitude of the decay constant, β, decreases with the increase in length of the wire. A highly delocalized π-electron cloud in the polyene chain appears to facilitate retention of the electronic coupling at large separations between the donor and acceptor centers. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem 109: 1302-1310, 2009.

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International Journal of Quantum Chemistry