Hydrogen-related defects in diamond: A comparison between observed and calculated FTIR spectra

A comprehensive and up-to-date compilation of observed and calculated hydrogen (H)-related peaks that occur in the near- and middle-infrared spectra of diamond is presented. The experimental database contains >300 observed peaks attributed to H-related impurities in natural diamond. The database of calculated peaks includes data from first-principles simulations of the FTIR spectra of different VxNyHz defects in diamond and contains >300 peaks that correspond to different C-H, N-H, and B-H vibrational modes for each VxNyHz defect. Less than ~10 % of observed H-related peaks have been assigned to specific defects. Consequently, the computational database was constructed to better understand the properties of different VxNyHz defects that may correspond to different observed peaks. In general, hydrogen-rich diamonds with a dominant Type Ib character and thus poorly aggregated N, show a larger number of low-intensity, H-related peaks compared to diamonds with a dominant Type Ia character. For example, ~51 % of observed H-related peaks are only observed in Type Ib diamonds, ~9 % of peaks are only observed in diamonds with a dominant Type Ia character and ~40 % of peaks are observed in both Type Ia and Type Ib diamonds. There is a major increase in the number of distinct H-related peaks in Type IaA + Ib diamonds compared to Type Ib diamonds suggesting N-aggregation processes responsible for the formation of A-centers may also produce many distinct VxNyHz defects capable of trapping H. There is a major decrease in the number of H-related peaks in Type IaA > Ib diamonds compared to Type IaA + Ib diamonds suggesting that many of the VxNyHz defects associated with the initial production of A-centers become unstable with increasing mantle residence time and the progressive loss of C-centers. These defects likely combine (or disaggregate and then re-combine) to form fewer, relatively more intense, H-related peaks observed in Type IaA > Ib diamonds. Many of these peaks persist through continued annealing in the mantle and are observed in Type IaA, IaAB, and IaB diamonds. Our data suggests that N and H incorporation are not correlated during diamond growth and that in the early stages of diamond residence, H is incorporated into many distinct VxNyHz defects that involve C- and A-centers. With continued residence and annealing, and the progressive formation A-centers and loss of C-centers, these defects aggregate to form relatively fewer, presumably more stable, VxNyHz defects such as VN3H.