title: Selective functionalization of the Si(100) surface by a bifunctional alkynylamine molecule: density functional study of the switching adsorption linkage. 2.
abstract: The reaction of the bifunctional organic molecule 1-(dimethylamino)-2-propyne (DMAP) on the Si(100) surface has been investigated by density functional calculations employing a two-dimer cluster model. We found that, once in the physisorbed dative bonded well (-20.0 kcal mol(-1)), DMAP can proceed via a number of pathways, involving the formation of Si-C sigma bonds, which lead to thermodynamically more stable configurations. We first considered the cycloaddition of the CC triple bond, leading to a Si-C di-sigma bonded product (-58.7 kcal mol(-1)), for which we computed an energy barrier of only 12.5 kcal mol(-1), consistently with the observed switching of DMAP adsorption linkage at 300 K. We also explored the dissociative pathway involving the methylene C-H bond cleavage on the dative bonded DMAP, leading to three adsorption products with one (-57.3 kcal mol(-1)) and three Si-C sigma bonds (-58.7 and -60.6 kcal mol(-1)). The energy barrier for this pathway is computed 24.7 kcal mol(-1) and may therefore compete at temperature above 300 K with the reaction pathway involving the addition of the alkyne unit.
authors.affiliation: Istituto CNR di Scienze e Tecnologie Molecolari (ISTM) c/o Dipartimento di Chimica, Università di Perugia, I-06123 Perugia, Italy. nunzi@thch.unipg.it
authors.forename: Francesca
authors.initials: F
authors.lastname: Nunzi
authors.forename: Antonio
authors.initials: A
authors.lastname: Sgamellotti
authors.forename: Nazzareno
authors.initials: N
authors.lastname: Re
mesh_terms: D000327:Adsorption; D000480:Alkynes / Q000737:chemistry*; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D007202:Indicators and Reagents; D008956:Models, Chemical; D012828:Silicones / Q000737:chemistry*; D013499:Surface Properties
chemical_list: D000480:Alkynes; D007202:Indicators and Reagents; D012828:Silicones; C011785:3-dimethylamino-1-propyne