Ab Initio Modeling of Amide-Stabilized, Oligo(etylene glycol)-Terminated Self-Assemblies: In-SAM Molecular Geometry, Orientation, and Hydrogen Bonding
2008 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 112, no 8, 1683-1687 p.Article in journal, Letter (Other academic) Published
Under the constraint that sulfur atoms form a hexagonal (×)R30° overlayer on the (111) gold surface, the optimized geometry of periodic arrays of HS(CH2)3CONH−(CH2CH2O)3H molecules has been found ab initio, by exploiting the BP86 exchange-correlation functional with 6-31G and “general” basis sets. The obtained data suggests that several prominent features of in-SAM molecular geometry and orientation stand out from conclusions based on single-molecule modeling. In particular, changing of amide-related dihedrals is shown to dominate in adjustment of molecular constituents to the assembly environment and to result in a substantial shortening of the hydrogen bond distance between nearest-neighbor amides. First demonstrated here, the full account to the intermolecular interaction within periodic arrays of amide-bridged, oligo(ethylene glycol)-terminated alkanethiolates forms a new platform for arguable modeling of SAM apparent properties.
Place, publisher, year, edition, pages
Washington, DC, USA: American Chemical Society (ACS), 2008. Vol. 112, no 8, 1683-1687 p.
IdentifiersURN: urn:nbn:se:liu:diva-42060DOI: 10.1021/jp711604hISI: 000253355300003Local ID: 60094OAI: oai:DiVA.org:liu-42060DiVA: diva2:262915