Ab-Initio Investigations on Hydrogen Dissociation and Cross-Linking of Hydrocarbon Chains of Self-Assembled Monolayers of Alkanes

First-principles calculations were carried out to study the structural and electronic properties of hydrocarbon chains of self-assembled monolayers with hydrogen dissociation. It was found that the incoming hydrogen could lead to the formation of H2 molecules by stripping the nearby hydrogen atoms in the chains and thereby leave the neighboring carbon atoms to be free radicals. Two parallel hydrocarbon chains with dangling bonds can form a direct C-C bond, i.e., cross-linking happens between the two chains, which is ascribed to a charge accumulation in the cross-linking region. The polymerization of short molecules into long hydrocarbon chains through a different cross-linking mode is also discussed.