We present an efficient particle–particle random
phase approximation
(ppRPA) approach that predicts accurate excitation energies of point
defects, including the nitrogen-vacancy (NV–) and
silicon-vacancy (SiV0) centers in diamond and the divacancy
center (VV0) in 4H silicon carbide, with errors of ±0.2
eV compared with experimental values. Starting from the (N + 2)-electron ground state calculated with density functional theory
(DFT), the ppRPA excitation energies of the N-electron
system are calculated as the differences between the two-electron
removal energies of the (N + 2)-electron system.
We demonstrate that the ppRPA excitation energies converge rapidly
with a few hundred canonical active-space orbitals. We also show that
active-space ppRPA has weak DFT starting-point dependence and is significantly
cheaper than the corresponding ground-state DFT calculation. This
work establishes ppRPA as an accurate and low-cost tool for investigating
excited-state properties of point defects and opens up new opportunities
for applications of ppRPA to periodic bulk materials.