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
Hauptverfasser: Atanasov, Mihail, Andreici Eftimie, Emiliana-Laura, Avram, Nicolae M, Brik, Mikhail G, Neese, Frank
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container_end_page 192
container_issue 1
container_start_page 178
container_title Inorganic chemistry
container_volume 61
creator Atanasov, Mihail
Andreici Eftimie, Emiliana-Laura
Avram, Nicolae M
Brik, Mikhail G
Neese, Frank
description 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.
doi_str_mv 10.1021/acs.inorgchem.1c02650
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