title: Stereoselective cycloaddition of 1,3-cyclohexadiene on Si(100): a simple algorithm for product identification based on secondary orbital interactions.
abstract: We consider the reaction of 1,3-cyclohexadiene (1,3-CHD) on Si(100) and show that the observed reactivity and stereoselectivity cannot be explained on the basis of thermodynamics. We postulate the existence of secondary orbital interactions (SOIs) and introduce a simple algorithm that examines all possible secondary interactions between the frontier orbitals of the molecule and the surface. We demonstrate using an orbital symmetry-based algorithm supported by DFT calculations that SOIs favor a particular molecular configuration, consistent with the experimental observations. The potential role of SOIs in controlling surface chemical reactions is discussed.
authors: School of Chemistry and Centre for Research on Adaptive Nanostructures and Nanodevices (CRANN), Trinity College Dublin, Dublin 2, Ireland.
authors: Peter M
authors: PM
authors: Ryan
authors: Lucile C
authors: LC
authors: Teague
authors: David E
authors: DE
authors: Meehan
authors: John J
authors: JJ
authors: Boland