First-Principles Study of Optical Absorption Energies, Ligand Field and Spin-Hamiltonian Parameters of Cr3+ Ions in Emeralds
Herein, we study the electronic structure, energies, and vibronic structure of optical d-d transitions of Cr3+ ions doped in beryl (Be3Si6Al2O18:Cr3+, emerald). A computational protocol is developed that combines periodic density functional theory (for modeling of the bulk crystalline lattice of eme...
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Veröffentlicht in: | Inorganic chemistry 2022-01, Vol.61 (1), p.178-192 |
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Hauptverfasser: | , , , , |
Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | Herein, we study the electronic structure, energies, and vibronic structure of optical d-d transitions of Cr3+ ions doped in beryl (Be3Si6Al2O18:Cr3+, emerald). A computational protocol is developed that combines periodic density functional theory (for modeling of the bulk crystalline lattice of emerald) and the multireference configuration interaction complete active space self-consistent field method supplemented with n-electron valence second-order perturbation theory (for the calculation of the energy levels, wave functions, and spin-Hamiltonian and ligand-field parameters of the trigonal Cr3+ centers in the [CrO6]9– clusters embedded in an extended point charge field). Ligand-field parameters were extracted from mapping the effective ligand-field Hamiltonian onto the full many-particle Hamiltonian from one side and from a direct fit to energies of computed d-d transitions on the other side. These have been analyzed using ab initio ligand-field theory. The quality of the theoretical predictions is critically assessed through a detailed comparison with the available experimental data. |
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ISSN: | 0020-1669 1520-510X |
DOI: | 10.1021/acs.inorgchem.1c02650 |