The reaction of molecular oxygen with the Si(111)-7 x 7 surface is investigated at room temperature using in situ scanning tunneling microscopy and surface stress measurements to reveal the quantitative relationship between site-specific oxygen coverage and a decrease in tensile surface stress. This relationship is described using a modified form of the reaction model originally proposed by Dujardin et al. We show that the decrease in tensile surface stress is greatest for the faulted subunits of the 7 x 7 cell and determine the stress signatures of different reaction products, including the absence of long-lived metastable species with a unique stress signature.

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.