One- and two-photon absorption properties of diamond nitrogen-vacancy defect centers: A theoretical study

The negatively charged nitrogen-vacancy defect center, (NV)(-), in diamond has been investigated theoretically for its one- and two-photon absorption properties involving the first excited state with the (3)A(2)-->(3)E transition. Time-dependent density functional theory (TD-DFT), configuration interaction with single excitation (CIS), and complete active space self-consistent field (CASSCF) were employed in this investigation along with the 6-31G(d) basis set. Diamond lattice models containing 24-104 carbon atoms were constructed to imitate the local environment of the defect center. TD-DFT calculations in large molecular cluster models (with 85 or more carbon atoms) predicted the vertical excitation energy quite consistent with the experimental absorption maximum. CASSCF calculations were feasible only for small cluster models (less than 50 carbon atoms) but yielded one-photon absorption (OPA) and two-photon absorption (TPA) cross sections somewhat larger than the experimental values obtained with linearly polarized incident light [T.-L. Wee et al., J. Phys. Chem. A 111, 9379 (2007)]. CIS calculations in larger cluster models showed a systematic overestimation of the excitation energy while just slightly underestimated the OPA cross section and overestimated the TPA cross section. The agreements between calculations and measurements suggest that the computational approaches established in this work are applicable to explore the optical properties of related defect centers in diamond as well.