Role of Adatoms in Organometallic Overlayer On-Surface Self-Assembly

Recent developments in microscopic methods such as Scanning Tunneling Microscopy (STM) provide direct insight into the chemical make up of technologically relevant self-assembled overlayers formed on-surface. Understanding the chemical mechanisms that drive such self-assembly, and how they compete to form a mixture of different overlayers under the same conditions remains a challenge. In this work, we will combine state-of-the-art STM with theoretical models based on density functional theory (DFT) and STM simulations to provide insight into the driving mechanisms behind the formation of different organometallic overlayers. Specifically, we will study the role of metal adatoms for promoting the formation of three-fold, four-fold, and six-fold junctions within Ph6(CN)2) on Au(111). This work will show that metal adatoms are accounted for in order to properly describe the coverage of competing overlayer types.