Analysis of bonding between conjugated organic molecules and noble metal surfaces using orbital overlap populations

Gerold M. Rangger, Lorenz Romaner, Oliver T. Hofmann, Georg Heimel, Michael G. Ramsey, Egbert Zojer

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The electronic structure of metal-organic interfaces is of paramount importance for the properties of organic electronic and single-molecule devices. Here, we use so-called orbital overlap populations derived from slab-type band-structure calculations to analyze the covalent contribution to the bonding between an adsorbate layer and a metal. Using two prototypical molecules, the strong acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) on Ag(111) and the strong donor 1H,1'H-[4,4']bipyridinylidene (HV0) on Au(111), we present overlap populations as particularly versatile tools for describing the metal-organic interaction. Going beyond traditional approaches, in which overlap populations are represented in an atomic orbital basis, we also explore the use of a molecular orbital basis to gain significant additional insight. On the basis of the derived quantities, it is possible to identify the parts of the molecules responsible for the bonding and to analyze which of the molecular orbitals and metal bands most strongly contribute to the interaction and where on the energy scale they interact in bonding or antibonding fashion.

Original languageEnglish
Pages (from-to)3481-3489
Number of pages9
JournalJournal of chemical theory and computation
Volume6
Issue number11
DOIs
Publication statusPublished - 9 Nov 2010

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Precious metals
noble metals
metal surfaces
Metals
orbitals
Molecules
Molecular orbitals
metals
molecules
molecular orbitals
Adsorbates
Band structure
Electronic structure
slabs
interactions
electronic structure
electronics
energy

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Cite this

Analysis of bonding between conjugated organic molecules and noble metal surfaces using orbital overlap populations. / Rangger, Gerold M.; Romaner, Lorenz; Hofmann, Oliver T.; Heimel, Georg; Ramsey, Michael G.; Zojer, Egbert.

In: Journal of chemical theory and computation, Vol. 6, No. 11, 09.11.2010, p. 3481-3489.

Research output: Contribution to journalArticleResearchpeer-review

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AU - Ramsey, Michael G.

AU - Zojer, Egbert

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