Edging towards an understanding of CH/CH2 on nanodiamonds. Regular and semi-regular polyhedra and diamond network models

Nano-diamonds have been observed in only a handful of circumstellar regions $10-100$\,\tiny{ A.U.} from moderately bright stars ($T_{\rm eff} \sim 8,000-10,000$\,K). They have also been extracted from primitive meteorites; some of these are clearly pre-solar, that is to say that they formed far from the solar system and therefore traversed the interstellar medium, where they must exist but, because we see no evidence of them, must be extremely well hidden. Our goal is to understand if it is possible to constrain the sizes and shapes of nano-diamonds in circumstellar media using the observed ratio, [CH]/[CH$_2$], of their surface CH$_2$ and CH infrared bands at $\simeq 3.43\,\mu$m and $\simeq 3.53\,\mu$m, respectively. We calculated the CH and CH$_2$ abundances on nano-diamonds using two approaches. The first assumes regular and semi-regular polyhedra (tetrahedra, octahedra, and cubes and their truncated forms). The second uses a diamond bonding network to derive the structures of tetrahedral and octahedral particles, and their truncated variants, and also of spherical nano-diamonds. As a function of the particle size and shape, and for the two different calculation methods, we derived the relative abundance ratio [CH]/[CH$_2$], which can then be weighted by their laboratory-measured infrared band intensities. The two methods give good agreement and indicate that the spread in values, over the different particle forms, is more that an order of magnitude for any size. We conclude that the ratio [CH]/[CH$_2$], and their infrared band ratio, strongly depend upon particle size and shape. For a given shape or size, the ratio can vary by more than an order of magnitude. It may therefore be difficult to constrain nano-diamond sizes using the observed $3-4\,\mu$m spectra alone. James Webb Space Telescope (JWST) mid-infrared spectra may help, but only if bands are size-specific.