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. [ABSTRACT FROM AUTHOR]