DFT STUDY OF THE FORMATION OF CH2=CF2 THROUGH BOTH METHYLENE INSERTION AND β-FLUORIDE ELIMINATION ON THE Ag(111) SURFACE

Abstract

Total energy calculations based on (1) density functional theory (DFT) in connection with ultrasoft pseudopotential and generalized gradient spin-polarized approximation (GGSA) and (2) the partial structural constraint path minimization (PSCPM) method have been used to investigate the energetically more favorable pathway for methylene ( CH 2) insertion into the Ag–CF 3 bond followed by β-fluoride elimination to generate an isolated CH 2= CF 2( g ) above the Ag(111) surface. The diffusion of the fcc-hollow site of CF 3( ads ) toward the bridge site of CH 2( ads ) is proposed as an energe*tically more favorable path for CH 2 insertion into the Ag–CF 3 bond to form the bridge site of CH 2 CF 3( ads ) on the Ag(111) surface. Then we proceed with β-fluoride elimination to form an isolated CH 2= CF 2( g ) and the bridge site of F (ads) on the Ag(111) surface. Our calculated energy barrier for β-fluoride elimination is 0.715 eV higher than that for CH 2 insertion on the Ag(111) surface. These calculated results imply that β-fluoride elimination rather than CH 2 insertion on the Ag(111) surface controls the CH 2= CF 2( g ) formation rate as observed from temperature-programmed reaction (TPR) experimental data. Finally, we attribute these different energy barriers to the different transition state structures — largely distorted seven-centered versus less distorted four-centered — involved in these two different processes.