Frontier orbital control of molecular conductance and its switching

Yuta Tsuji, Roald Hoffmann

Research output: Contribution to journalArticlepeer-review

64 Citations (Scopus)

Abstract

For transmission of electrons through a π system, when the Landauer theory of molecular conductance is viewed from a molecular orbital (MO) perspective, there obtains a simple perturbation theoretic dependence, due to Yoshizawa and Tada, on a) the product of the orbital coefficients at the sites of electrode attachment, and b) the MO energies. The frontier orbitals consistently and simply indicate high or low transmission, even if other orbitals may contribute. This formalism, with its consequent reinforcement and/or interference of conductance, accounts for the (previously explained) difference in direct vs. cross conjugated transmission across an ethylene, as well as the comparative ON/OFF ratios in the experimentally investigated dimethyldihydropyrene and dithienylethene-type single-molecule switches. A strong dependence of the conductance on the site of attachment of the electrodes in a π system is an immediate extrapolation; the theory then predicts that for some specified sites the switching behavior will be inverted; i.e. the "open" molecular form of the switch will be more conductive. The phase and amplitude of the frontier molecular orbitals at the sites that are connected to electrodes play an essential role in determining transmission of electrons through a π system. When applied to two diarylethene switches, theory then predicts that for some specified sites the switching behavior will be inverted; that is, the "open" molecular form of the switch will be more conductive.

Original languageEnglish
Pages (from-to)4093-4097
Number of pages5
JournalAngewandte Chemie - International Edition
Volume53
Issue number16
DOIs
Publication statusPublished - Apr 14 2014
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Fingerprint Dive into the research topics of 'Frontier orbital control of molecular conductance and its switching'. Together they form a unique fingerprint.

Cite this