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*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


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
Issue number11
Publication statusPublished - 9 Nov 2010

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry


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