From Mono- to Hexa-Interstitials: Computational Insights into Carbon Defects in Diamond

We present a comprehensive first-principles investigation of carbon self-interstitial defects in diamond, ranging from mono- to hexa-interstitial complexes. By quantum mechanical density functional theory, empowered by interatomic potential models, we efficiently sample the complex configurational landscape and identify both known and previously unreported defect geometries. Our results reveal a pronounced energetic driving force for aggregation: the formation energy per interstitial decreases systematically from isolated split interstitials to compact multi-interstitial clusters, with the tetra-interstitial platelet emerging as a particularly stable structural motif. Additionally, charge analysis indicates that the predominantly covalent bonding in diamond becomes more polar within the defect centers. Analysis of defect energy levels shows that only the investigated mono-, di-, penta-, and hexa-interstitial complexes introduce in-gap electronic states, whereas the tri- and tetra-interstitial clusters are electronically inert. Vibrational spectroscopies further reveal that self-interstitials generate characteristic signatures. Short carbon-carbon bonds inside the defect cores give rise to high-frequency vibrational modes between 1375 and 1925 cm$^{-1}$, which are strongly IR-active but exhibit weak Raman activity. Through a systematic analysis of metastable configurations, we identify the 3H defect center as a neutral di-interstitial defect. Based on this identification, we further suggest that the TR12 center may arise from a 3H-containing defect like a metastable hexa-interstitial configuration. Taken together, these findings provide a coherent picture of the structural, electronic, and vibrational characteristics of carbon self-interstitials and establish a robust framework for their experimental identification.