Selective functionalization of the Si(100) surface by a bifunctional alkynilamine molecule: A density functional study of the switching adsorption linkage

The reaction of the bifunctional organic molecule 1-dimethylamino-2-propyne (DMAP) on the Si(100) surface has been investigated by density functional calculations on a one-dimer cluster model. We found that, once in the physisorbed dative bonded well (−22.1 kcal mol−1), DMAP can proceed to react via a number of pathways. We first considered the cycloaddition of the CC triple bond, leading to Si–C di-σ bonded product (−58.6 kcal mol−1), computing an energy barrier of 33.1 kcal mol−1. We considered also possible dissociative pathways of dative bonded DMAP, i.e., methylene C–H, methyl C–H or N–CH3 bond cleavage.