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

摘要

The reaction of acrylonitrile with the C(001)-2×1 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 nonpoiar 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+2Jcc 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.