Ghost transmission: How large basis sets can make electron transport calculations worse

Carmen Herrmann, Gemma C. Solomon, Joseph E. Subotnik, Vladimiro Mujica, Mark A Ratner

Research output: Contribution to journalArticle

60 Citations (Scopus)

Abstract

The Landauer approach has proven to be an invaluable tool for calculating the electron transport properties of single molecules, especially when combined with a nonequilibrium Green's function approach and Kohn-Sham density functional theory. However, when using large nonorthogonal atom-centered basis sets, such as those common in quantum chemistry, one can find erroneous results if the Landauer approach is applied blindly. In fact, basis sets of triple-zeta quality or higher sometimes result in an artificially high transmission and possibly even qualitatively wrong conclusions regarding chemical trends. In these cases, transport persists when molecular atoms are replaced by basis functions alone ("ghost atoms"). The occurrence of such ghost transmission is correlated with low-energy virtual molecular orbitals of the central subsystem and may be interpreted as a biased and thus inaccurate description of vacuum transmission. An approximate practical correction scheme is to calculate the ghost transmission and subtract it from the full transmission. As a further consequence of this study, it is recommended that sensitive molecules be used for parameter studies, in particular those whose transmission functions show antiresonance features such as benzene-based systems connected to the electrodes in meta positions and other low-conducting systems such as alkanes and silanes.

Original languageEnglish
Article number024103
JournalJournal of Chemical Physics
Volume132
Issue number2
DOIs
Publication statusPublished - 2010

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ghosts
electrons
Atoms
Electron transport properties
atoms
Silanes
Quantum chemistry
Molecules
Alkanes
quantum chemistry
Molecular orbitals
Benzene
Green's function
silanes
alkanes
Density functional theory
Electron Transport
molecules
molecular orbitals
Green's functions

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Ghost transmission : How large basis sets can make electron transport calculations worse. / Herrmann, Carmen; Solomon, Gemma C.; Subotnik, Joseph E.; Mujica, Vladimiro; Ratner, Mark A.

In: Journal of Chemical Physics, Vol. 132, No. 2, 024103, 2010.

Research output: Contribution to journalArticle

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