Failure of perturbative DFT-Derived STM images of organic molecules on semiconductor surfaces

Robin L. Hayes, Mark Tuckerman

Research output: Contribution to journalArticle

Abstract

Tersoff-Hamann and Bardeen perturbation theory derived empty-state STM images of the [4 + 2] intradimer adduct of 1,3-cyclohexadiene (CHD) adsorbed on Si(100)-2 × 1 using a density functional description of the electronic structure appear to capture the π* CdC orbital observed experimentally but ultimately produce images dominated by the CH 2 groups. Neither averages over finite temperature structures nor use of W(110) tips with O or Si adsorbed on the apex yield the correct image. Strong tip-CHD interactions substantially lower the energy of the π* orbital relative to the Fermi energy and change the CHD geometry. In addition to perturbing the CdC bond, it is found that the tip pushes aside the CH 2 groups. The former electronic effect enhances the prominence of the π* orbital, while the latter geometric effect suppresses contributions from the remainder of the CHD.

Original languageEnglish (US)
Pages (from-to)15102-15108
Number of pages7
JournalJournal of Physical Chemistry C
Volume114
Issue number35
DOIs
StatePublished - Sep 9 2010

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Fermi level
Discrete Fourier transforms
Electronic structure
Semiconductor materials
orbitals
Molecules
Geometry
methylidyne
molecules
Temperature
adducts
apexes
perturbation theory
electronic structure
energy
geometry
electronics
1,4-cyclohexadiene
interactions
temperature

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Failure of perturbative DFT-Derived STM images of organic molecules on semiconductor surfaces. / Hayes, Robin L.; Tuckerman, Mark.

In: Journal of Physical Chemistry C, Vol. 114, No. 35, 09.09.2010, p. 15102-15108.

Research output: Contribution to journalArticle

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