The optical spectra of neutral oxygen vacancies ($F^0$ centers) in the bulk MgO lattice was investigated using density matrix embedding theory. The impurity Hamiltonian was solved with the complete active space self-consistent field (CAS-DMET) and second-order n-electron valence state perturbation theory (NEVPT2-DMET) multireference methods. To estimate defect-localized vertical excitation energies at the non-embedding and thermodynamic limits, a double extrapolation scheme was employed. The extrapolated NEVPT2-DMET vertical excitation energy value of 5.24 eV agrees well with the experimental absorption maxima at 5.03 eV, whereas the excitation energy value of 2.89 eV at the relaxed triplet defect localized state geometry overestimates the experimental emission at 2.4 eV by only nearly 0.5 eV, indicating the involvement of triplet-singlet decay pathway.
Optical Properties of Neutral F Centers in Bulk MgO with Density Matrix Embedding
The basis set and active space details, procedure to vary the embedding subspace, excitation energies using different numbers of embedding orbitals for all the supercells and total energies are available in the Supporting Information.