An ab initio effective solid-state photoluminescence by frequency constraint of cluster calculation

Measuring the photoluminescence of defects in crystals is a common experimental technique for analysis and identification. However, current theoretical simulations typically require the simulation of a large number of atoms to eliminate finite-size effects, which discourages computationally expensive excited state methods. We show how to extract the room-temperature photoluminescence spectra of defect centers in bulk from an ab initio simulation of a defect in small clusters. The finite-size effect of small clusters manifests as strong coupling to low frequency vibrational modes. We find that removing vibrations below a cutoff frequency determined by constrained optimization returns the main features of the solid-state photoluminescence spectrum. This strategy is illustrated for the negatively charged nitrogen vacancy defect in diamond (NV −) presenting a connection between defects in solid state and clusters; the first vibrationally resolved ab initio photoluminescence spectrum of an NV − defect in a nanodiamond; and an alternative technique for simulating photoluminescence for solid-state defects utilizing more accurate excited state methods.