Nonalternant aromatic π-electron systems show promises for surface functionalization due to
their unusual electronic structure. Based on our previous experiences for metal surfaces, we
investigate the adsorption structures, adsorption dynamics and bonding characteristics of
azulene and its alternant aromatic isomer naphthalene on the Si(001) surface. Using a
combination of density functional theory, ab initio molecular dynamics, reaction path
sampling and bonding analysis with the energy decomposition analysis for extended systems,
we show that azulene shows direct adsorption paths into several, strongly bonded chemisorbed
final structures with up to four covalent carbon–silicon bonds which can be described in a
donor–acceptor and a shared-electron bonding picture nearly equivalently. Naphthalene also
shows these tetra-σ-type bonding structures in accordance with an earlier study. But the
adsorption path is pseudo-direct here with a precursor intermediate bonded via one aromatic
ring and strong indications for a narrow adsorption funnel. The four surface-adsorbate bonds
formed lead for both adsorbates to a strong corrugation and a loss of aromaticity.
| Identifer | oai:union.ndltd.org:DRESDEN/oai:qucosa:de:qucosa:85135 |
| Date | 03 May 2023 |
| Creators | Kreuter, Florian, Tonner, Ralf |
| Publisher | IOP Publishing |
| Source Sets | Hochschulschriftenserver (HSSS) der SLUB Dresden |
| Language | English |
| Detected Language | English |
| Type | info:eu-repo/semantics/publishedVersion, doc-type:article, info:eu-repo/semantics/article, doc-type:Text |
| Rights | info:eu-repo/semantics/openAccess |
| Relation | 1361-648X, 444003 |
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