Abstract
The chemistry of organic adsorbates on surfaces is often discussed in terms of Pauli repulsion as limiting factor regarding the packing of molecules. Here we show that the attractive part of the van der Waals potential can be similarly decisive. For the semiconductor surface Si(001), an already covalently bonded molecule of cyclooctyne steers a second incoming molecule via dispersion interactions onto the neighbouring adsorption site. This helps in understanding the nonstatistical pattern formation for this surface–adsorbate system and hints toward an inclusion of dispersion attraction as another determining factor for surface adsorption.
Highlights
The creation of organic/inorganic interfaces is one of the main endeavours in enhancing the application range of modern electronic devices for silicon-based technology [1,2]
Since both the product and the pathway are influenced by dispersion interactions, the question arises if these forces can tweak the potential energy surface (PES) in a way to steer the second adsorbate onto a certain position on the surface
We have shown that dispersion effects are important for the thermodynamic stability of molecule–adsorbate complexes but they crucially influence the adsorption path
Summary
The creation of organic/inorganic interfaces is one of the main endeavours in enhancing the application range of modern electronic devices for silicon-based technology [1,2]. For the semiconductor surface Si(001), an already covalently bonded molecule of cyclooctyne steers a second incoming molecule via dispersion interactions onto the neighbouring adsorption site. The results show that dispersive interactions can be decisive in building novel organic structures on surfaces by tweaking the potential energy surface.
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