Quantum behavior of hydrogen-vacancy complexes in diamond

摘要： Hydrogen plays an essential role in the growth process of artificial diamond and can easily form complexes with lattice vacancies. Despite substantial efforts to resolve the electronic structure and the ground-state properties of the hydrogen-vacancy (HV) center, the final remarks are ambiguous, while the complexes of vacancy with two and more hydrogen atoms remain unexplored. In this paper, we used spin-polarized, hybrid density-functional theory method to investigate electronic structure and magneto-optical properties of various hydrogen-vacancy clusters in diamond. Our theoretical results indicate a very strong tendency toward the formation of HnV complexes up to four hydrogen atoms that are mostly electrically and optically active centers. One of the investigated defects introduce highly correlated electronic states that pose a challenge for density-functional theory and, therefore, require special treatment when charge- and spin-density-related properties are determined. We introduced an extended Hubbard model Hamiltonian with fully ab initio provided parameters to analyze the complex electronic structure of highly correlated H2V0 defects. The role of quantum tunneling of hydrogen in HV center and its impact on the hyperfine structure was discussed. We demonstrate that experimentally observed HV1? center is similar to well-known NV1?, i.e., I) it possesses triplet 3A ground state and 3E excited state in C3v symmetry; II) the calculated zero-phonon line is 1.71 eV (1.945 eV for NV1?). A detailed experimental reinvestigation based on optically detected electron paramagnetic resonance spectroscopy is suggested to verify whether the HV1? center has metastable singlet shelving states between the ground and excited state triplets and, as a result, whether it may exhibit a spin-selective decay to the ground state.