Reaction Pathways for the Additions of Triplet Carbene, Silylene, Germylene and Nitrene onto the Diamond (100) Surface: A Theoretical Investigation

Abstract

The additions of triplet carbene (CH2), silylene (SiH2), germylene (GeH2), and nitrene (NH) onto the diamond (100) surface have been investigated by means of density functional theory in conjunction with effective cluster models. The calculated reaction energies and reaction pathways have demonstrated that the reaction profiles for the additions of triplet species onto the diamond (100) surface is clearly different from those for singlet ones. Namely, triplet CH2, SiH2, GeH2, and NH are inclined to form the one-end-sided species by attaching to only one carbon of the surface dimer of diamond (100). Hence, the other carbon of the surface dimer will be open, which can be potentially used for anchoring other functional groups. This is in distinct contrast to the profile for the additions of singlet ones onto diamond (100) in which the as-formed surface species feature a three-membered ring structure. The results illustrate that the addition profiles of CH2s, SiH2s, GeH2s, and NHs onto the diamond (100) surface could be appropriately tuned depending on their spin states.