Length-Dependence of Intramolecular Electron Transfer in Sigma-Bonded Rigid Molecular Rods: An ab initio Molecular Orbital Study

Abstract

The dependence of electron transfer (ET) coupling element, V?sub AB!, on the length of rigid-rod-like systems consisting of bicyclo1.1.1pentane (BCP), cubane (CUB), and bicyclo2.2.2octane (BCO) monomers, has been investigated with the use of ab initio Hartree-Fock (HF) method employing Marcus-Hush two-state (TS) model. The value of V?sub AB! decreases exponentially with increase in the number of the cage units of the sigma-bonded molecules. The calculated decay constant, beta, shows good agreement with previously reported data. For molecular length >or=15 AA, the value of V?sub AB! becomes negligibly small, suggesting complete suppression of the through bond direct tunneling contribution to ET process.

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Document Details

Document Type
Technical Report
Publication Date
Jan 10, 2002
Accession Number
ADA435173

Entities

People

  • Ranjit Pati
  • Shashi P Karna

Organizations

  • University of New Mexico

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  • Air Force
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  • Electron Transfer
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Fields of Study

  • Chemistry

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