A van der Waals DFT study of chain length dependence of alkanethiol adsorption on Au(111): Physisorption vs.chemisorption

TL;DR

This study uses van der Waals corrected DFT to analyze how chain length influences the adsorption modes of alkanethiols on Au(111), revealing the transition between physisorption and chemisorption and the structural factors involved.

Contribution

It provides a systematic DFT investigation into chain length effects on alkanethiol adsorption, highlighting the transition mechanisms between lying down and standing up phases.

Findings

Longer chains favor standing up monolayer structures.

Strong alkyl chain-gold interactions can force molecules to lie parallel to the surface.

Coverage and size influence chain-chain electronic interactions.

Abstract

The energetics and structures of physisorbed and chemisorbed alkanethiols on Au(111) have been systematically investigated up to 10 carbon atoms using van der Waals (vdW) corrected density functional theory (DFT) calculations. The role of chain length, tilting angle and coverage on the adsorption characteristics have been examined to elucidate the energetics and plausible transformation mechanisms between lying down and standing up phases. Coverage and size dependent chain-chain electronic interactions counteract with the alkyl chain-gold surface interactions and the surface relaxation of the metal in the formation of standing up monolayer structures. For the striped phases of long chain alkanethiols, however, our calculations on decanethiol indicates alkyl chain-gold surface interactions to be strong enough to force the molecule to be perfectly parallel to the surface by lifting a gold atom up, in agreement with the proposed models for this film in the literature.