The electronic g-tensor dependence on the size, shape, and surface functionalization of nanodiamonds (NDs) is theoretically investigated by selecting dangling bonds and single substitutional nitrogen atoms as a main source of the unpaired electrons. The performed g-tensor calculations reveal that aforementioned paramagnetic impurities introduced into octahedrally shaped ND of C84H64 size behave in a very similar manner as those embedded into a smaller octahedral model of C35H36 size. Since cubic and tetrahedral NDs—C54H48 and C51H52—demonstrate a wider range of g-shift values than octahedral systems, the g-tensor dependence on different shapes can be considered as more pronounced. However, a different surface functionalization scheme, namely, fluorination, results in a much larger variation of the g-shifts, pointing to a significant impact the F atoms have on the local environment of the unpaired electrons in C35F36. A partial surface functionalization of C35H36 with benzoic acid and aniline groups indicates that, in some special cases, these linkers might induce a noticeable spin density redistribution which in turn substantially modifies the g-shift values of the system. Additional infrared (IR) spectra calculations show that some of paramagnetic defects in C35H36 and C35F36 possess clearly expressed signatures which could be useful while analyzing the experimental IR spectra of NDs.

Supplementary Material

You do not currently have access to this content.