Local Excitations of a Charged Nitrogen Vacancy in Diamond with Multireference Density Matrix Embedding Theory
At a Glance
Section titled āAt a Glanceā| Metadata | Details |
|---|---|
| Publication Date | 2023-05-01 |
| Journal | The Journal of Physical Chemistry Letters |
| Authors | Soumi Haldar, Abhishek Mitra, Matthew R. Hermes, Laura Gagliardi |
| Institutions | University of Chicago, Argonne National Laboratory |
| Citations | 28 |
Abstract
Section titled āAbstractāWe 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 ā¼2.18 eV and ā¼1.26 eV, respectively. This is the first application of pDMET to a charged periodic system and the first investigation of the NV<sup>-</sup> defect using NEVPT2 for periodic supercell models.