Adsorption and Reaction of Terephthaloyl Chloride on Ag(111): X-ray Photoelectron Spectroscopy and Density Functional Theory Investigations

Abstract

The adsorption and reaction of terephthaloyl chloride (TPC) on a Ag(111) surface was investigated with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations. Below 120 K, TPC forms multilayers without reacting with the Ag(111) substrate. Multilayer desorption starts above 120 K and is accompanied by a chemical reaction between the TPC molecules and the Ag surface. This reaction involves scission of the carbon–chlorine bond, resulting in the formation of adsorbed chlorine atoms and a p-phenylene dicarbonyl (pPDC) species. This molecular fragment is stable at room temperature and does not undergo further decomposition, presumably due to stabilization by adsorbate–substrate interactions and/or oligomerization. The DFT calculations confirm that pPDC is a possible intermediate or final reaction product and show that the two carbonyl C atoms form covalent bonds to the Ag substrate.