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Length‐dependence of electron transfer coupling matrix in polyene wires: Ab initio molecular orbital theory study
Author(s) -
Mallick Govind,
Karna Shashi P.,
He Haiying,
Pandey Ravindra
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21927
Subject(s) - polyene , ab initio , chemistry , delocalized electron , molecular physics , molecular orbital , molecular wire , ab initio quantum chemistry methods , computational chemistry , electron transfer , coupling constant , acceptor , electron , molecule , atomic physics , physics , condensed matter physics , quantum mechanics , organic chemistry
The electron transfer (ET) properties of π‐electron conjugated quasi‐one‐dimensional molecular wires, consisting of polyene, [>CC<] 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‐ trans ‐butadiene 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. Published 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009