Self-assembled monolayers on Au(111) have outstanding chemical, electrical, and optical properties, and Au adatoms seem to play a key role in these properties. Still, the fundamental understanding of adatom transport inside the self-assembled structure is very thin. In this paper we use first-principles calculations to reveal new details about the migration mechanism of Au adatoms in the presence of a CH3S self-assembled structure on Au(111). We study the inclusion of Au adatoms inside a well-packed (√3 × √3)-R30°-CH3S self-assembled lattice and present atomistic models supporting adatom migration by means of a hopping mechanism between pairs of CH3S species. Our calculations reveal that the transport of Au adatoms is slowed down inside the molecular network where the kinetic barrier for adatom migration is larger than on the clean Au surface. We attribute the hindered mobility of Au adatoms to the fact that adatom transport involves the breaking and making of Au-S bonds. Our results form a basis for further understanding the role played by defect transport in the properties of molecular assemblies.
We employ first-principles density functional theoretical calculations to address the inclusion of gold (Au) clusters in a well-packed CH 3 S self-assembled lattice. We compute CH 3 S adsorption energies to quantify the energetic stability of the self-assembly and gold adsorption and dissolution energies to characterize the structural stability of a series of Au clusters adsorbed at the SAM-Au interface. Our results indicate that the inclusion of Au clusters with less than four Au atoms in the SAM-Au interface enhances the binding of CH 3 S species. In contrast, larger Au clusters destabilize the self-assembly. We attribute this effect to the low-coordinated gold atoms in the cluster. For small clusters, these low-coordinated sites have significantly different electronic properties compared to larger islands, which makes the binding with the self-assembly energetically more favorable. Our results further indicate that Au clusters in the SAM-Au interface are thermodynamically unstable and they will tend to dissolve, producing Au adatoms incorporated in the self-assembly in the form of CH 3 S-Au-SCH 3 species. This is due to the strong S-Au bond which stabilizes single Au adatoms in the self-assembly. Our results provide solid insight into the impact of adatom islands at the CH 3 S-Au interface.
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