A DFT Study of the 1,3-Dipolar Cycloadditions on the C(100)-2 × 1 Surface

Abstract

The 1,3-dipolar cycloadditions (1,3-DCs) of a series of 1,3-dipolar molecules onto the C(100)-2 x 1 surface have been investigated by means of hybrid density functional B3LYP method in combination with cluster model approach. It was found that 1,3-DCs on the C(100)-2 x 1 surface are more favorable over their molecular analogues both thermodynamically and kinetically. The enhancement of the reactivity on the surface due to the reduced overlap between the p(pi) orbitals of the surface C=C dimer should be important for the semiconductor industry because it might lead to a breakthrough in the fabrication of diamond films at low temperature.

Curved Pi-Conjugation, Aromaticity, and the Related Chemistry of Small Fullerenes (<C60) and Single-Walled Carbon Nanotubes

“…b Data obtained by two-layered ONIOM(B3LYP/6-31G*:AM1) calculations. c Data obtained at the B3LYP/6-31+G* level of theory (see ref ).…”

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

“…Indeed, recently, great effort has been devoted to understanding how organic molecules react with the surfaces of diamond. [13][14][15][16][17][18][19][20][21][22] For instance, experimentally, Hovis et al 13 carefully investigated the nature of [2+2] cycloaddition reaction on C, Si, and Ge surfaces, they predicted that cycloaddition reactions analogous to those observed previously on Si and Ge surfaces also take place on diamond surfaces; the lower reaction probability on diamond (001) is likely associated with its larger band gap and the absence of dimer tilting. 13 Theoretically, it was predicted that 1,3-dipolar cycloadditions of a series of 1,3-dipolar molecules onto the C(100) surface are much more favorable over their molecular analogues both thermodynamically and kinetically.…”

Functionalization of diamond (001)‐2 × 1 surface by cycloaddition of 1,3‐cyclohexadiene: A theoretical study

“…For instance, experimentally, Hovis et al carefully investigated the nature of [2 + 2] cycloaddition reaction on C, Si, and Ge surfaces, they predicted that cycloaddition reactions analogous to those observed previously on Si and Ge surfaces also take place on diamond surfaces; the lower reaction probability on diamond (001) is likely associated with its larger band gap and the absence of dimer tilting 13. Theoretically, it was predicted that 1,3‐dipolar cycloadditions of a series of 1,3‐dipolar molecules onto the C (100) surface are much more favorable over their molecular analogues both thermodynamically and kinetically 14, 15. Similarly, Long et al 16 studied the hydroboration of three allotropes of carbon with borane, they predicted that the hydroboration of C (001)‐2 × 1 occurs readily and the as‐hydroborated carbonous materials can be good starting points for further chemical modification and manipulation.…”

“…Surface reactions of unsaturated organic compounds with the diamond (001)‐2 × 1 reconstructed surface have been good examples for both theory and experiment. Indeed, recently, great effort has been devoted to understanding how organic molecules react with the surfaces of diamond 13–22. For instance, experimentally, Hovis et al carefully investigated the nature of [2 + 2] cycloaddition reaction on C, Si, and Ge surfaces, they predicted that cycloaddition reactions analogous to those observed previously on Si and Ge surfaces also take place on diamond surfaces; the lower reaction probability on diamond (001) is likely associated with its larger band gap and the absence of dimer tilting 13.…”