Local Excitations of a Charged Nitrogen Vacancy in Diamond with Multireference Density Matrix Embedding Theory

We investigate the negatively charged nitrogen-vacancy center in diamond using periodic density matrix embedding theory (pDMET). To describe the strongly correlated excited states of this system, the complete active space self -consistent field (CASSCF) followed by n-electron valence state second-order perturbation theory (NEVPT2) was used as the impurity solver. Since the NEVPT2-DMET energies show a linear dependence on the inverse of the size of the embedding subspace, we performed an extrapolation of the excitation energies to the nonembedding limit using a linear regression. The extrapolated NEVPT2-DMET first triplet-triplet excitation energy is 2.31 eV and that for the optically inactive singlet-singlet transition is 1.02 eV, both in agreement with the experimentally observed vertical excitation energies of-2.18 eV and-1.26 eV, respectively. This is the first application of pDMET to a charged periodic system and the first investigation of the NV- defect using NEVPT2 for periodic supercell models.

Automated summary

In this study, we investigated the negatively charged nitrogen-vacancy center in diamond using periodic density matrix embedding theory (pDMET). To accurately describe the strongly correlated excited states of the system, we utilized the complete active space self-consistent field (CASSCF) method followed by n-electron valence state second-order perturbation theory (NEVPT2) as the impurity solver. By extrapolating the excitation energies to the nonembedding limit using linear regression, we obtained the first triplet-triplet excitation energy of 2.31 eV and the singlet-singlet transition energy of 1.02 eV, both in agreement with experimental observations. This is the first application of pDMET to a charged periodic system and the first investigation of the NV- defect using NEVPT2 for periodic supercell models.