Density Functional Theory Investigation of Product Distribution following Reaction of Acrylonitrile on Diamond (001)-2×1 Surface

Abstract

The reaction of acrylonitrile with the C(001)-2 x 1 surface has been investigated by employing density functional cluster model calculations. The calculations revealed eight possible reaction pathways for acrylonitrile with the surface dimer. Full geometry optimized structures were obtained for all adducts, including intra- and interdimer reaction products. These results were analyzed in terms of both the total energy values and the detailed optimized geometries. We find that the reaction of acrylonitrile with the diamond (001) surface occurs primarily through its nonpolar C=C group and the intradimer [2+2](cc) product is the dominant product. All these results are in good agreement with the experimental work by Schwartz. It is noteworthy that the isomerization process plays an important role in the chemisorption process. Both intradimer [4+2] product and interdimer [2+2](cc) product can isomerize to the intradimer [2+2](cc) product. The present study shows that the isomerization between intradimer [4+2] product and intradimer [2+2](cc) product is slightly favorable over the direct path to formation of the intradimer [2+2](cc) product.

First-principles investigation of C60molecule adsorption on a diamond (1 0 0)-2 × 1 surface

“…The other is that, unlike C 60 on a Si(1 0 0)-2 × 1 surface where the most stable adsorption site is at the T4 site with T4(c) [12], the most stable adsorption of C 60 is on the R1 site with R1(e) configuration. In addition, we found that the adsorption undergoes similar Diels-Alder type of cycloaddition reactions on the surface, which have been found in adsorptions of small unsaturated organic molecules on semiconductor surfaces [26].…”