Mechanisms of molecular electronic rectification through electronic levels with strong vibrational coupling

Publication: Research - peer-reviewJournal article – Annual report year: 2002

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We present a new view and an analytical formalism of electron flow through a donor-acceptor molecule inserted between a pair of metal electrodes. The donor and acceptor levels are strongly coupled to an environmental nuclear continuum. The formalism applies to molecular donor-acceptor systems both in vacuum or air, and in aqueous solution under electrochemical potential control. Multifarious patterns of rectified electron flow from the negatively to the positively biased electrode arise. The electronic interaction between the donor and acceptor fragments, mutually and with the electrodes, can be weak, corresponding to the fully diabatic limit. The rectification process then reduces to a sequence of vibrationally relaxed single-electron transfer steps. In the limits where the interactions are strong, denoted as the partially and fully adiabatic limits, the character of the rectification process is different, and electron flow proceeds coherently, without vibrational relaxation. In still another class of mechanisms the electronic level broadening of either donor or acceptor from the adjacent electrode is so strong that it is comparable to the vibrational broadening. The process then reduces to a three-level transition similar to STM of large redox molecules. Recent data for rectification in hexadecyl-quinolinium tricyanodimethanide monolayers by Metzger and co-workers [J. Am. Chem. Soc. 119, 10455 (1997); Acc. Chem. Res. 32, 950 (1999)], are discussed in terms of the reported views and formalism.
Original languageEnglish
JournalJournal of Chemical Physics
Publication date2002
Volume116
Issue5
Pages2149-2165
ISSN0021-9606
DOIs
StatePublished

Bibliographical note

Copyright (2002) American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.

CitationsWeb of Science® Times Cited: 41

Keywords

  • LONG-RANGE, CURRENT-VOLTAGE CHARACTERISTICS, WIRES, LANGMUIR-BLODGETT-FILMS, ELECTRICAL RECTIFICATION, RIGID FUSED OLIGOPORPHYRINS, SCANNING-TUNNELING-MICROSCOPY, CONDUCTANCE QUANTIZATION, SELF-ASSEMBLED MONOLAYER, NEGATIVE DIFFERENTIAL RESISTANCE
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