Local Excitations of a Charged Nitrogen Vacancy in Diamond with Multireference Density Matrix Embedding Theory
We 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-ord...
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Veröffentlicht in: | The journal of physical chemistry letters 2023-05, Vol.14 (18), p.4273-4280 |
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Hauptverfasser: | , , , |
Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | We 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 ∼2.18 eV and ∼1.26 eV, respectively. This is the first application of pDMET to a charged periodic system and the first investigation of the NV– defect using NEVPT2 for periodic supercell models. |
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ISSN: | 1948-7185 1948-7185 |
DOI: | 10.1021/acs.jpclett.3c00551 |