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Quantum mechanical and hybrid quantum mechanical/molecular mechanical (QM/MM) cluster models have been used to investigate possible reaction mechanisms whereby gas phase NHx (x = 0-2), CNHx (x = 0, 1) and OH radicals can add to, and incorporate in, a C-C dimer bond on the C(100):H 21 diamond surface during chemical vapor deposition from microwave activated C/H containing gas mixtures containing trace amounts of added N or O. Three N incorporation routes are identified, initiated by N, NH and CN(H) addition to a surface radical site, whereas only OH addition was considered as the precursor to O incorporation. Each is shown to proceed via a ring-opening/ring-closing reaction mechanism analogous to that identified previously for the case of CH3 addition (and CH2 incorporation) in diamond growth from a pure C/H plasma. Based on the relative abundances of N atoms and NH radicals close to the growing diamond surface, the former is identified as the more probable carrier of the N atoms appearing in CVD grown diamond, but fast H-shifting reactions post-addition encourage the view that NH is the more probable migrating and incorporating species. CN radical addition is deemed less probable, but remains an intriguing prospect since, if the ring-closed structure is reached, this mechanism has the effect of adding two heavy atoms, with the N atom sitting above the current growth layer and thus offering a potential nucleation site for next-layer growth.
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Diamond. A crystalline form of carbon that occurs as hard, colorless or tinted isomeric crystals. It is used as a precious stone, for cutting glass, and as bearings for delicate mechanisms. (From Grant & Hackh's Chemical Dictionary, 5th ed)
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RNA that has catalytic activity. The catalytic RNA sequence folds to form a complex surface that can function as an enzyme in reactions with itself and other molecules. It may function even in the absence of protein. There are numerous examples of RNA species that are acted upon by catalytic RNA, however the scope of this enzyme class is not limited to a particular type of substrate.
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