Optical absorption spectra and g factor of MgO: Mn2+explored by ab initio and semi empirical methods

Eftimie, Emiliana Laura Andreici; Avram, C.N.; Brik, M.G.; Avram, N.M.

doi:10.1016/j.jpcs.2017.10.033

Cited by 12 publications

(6 citation statements)

References 45 publications

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“…Details about how to generate the embedded host environment are now included in Section 7 of the Supporting Information. The embedded cluster approximation has been used extensively in a number of previous papers. − …”

Section: Computational Protocolmentioning

confidence: 99%

“…The aim of this study is to theoretically investigate the optical absorption energies, vibrational band shapes, LFPs (LF splitting parameter Δ = 10 Dq ; the Racah two-electron repulsion parameter B ; the Wybourne B 20 , B 40 , and B 43 parameters; e σ and e π parameters of the angular overlap model (AOM) , ), and SHPs (g-factors, g x = g y = g ⊥ , g z = g ∥ , and the axial zero-field splitting (ZFS) parameter, D ) in emeralds by means of first-principles techniques. A pragmatic two-step methodology − combines the DFT supercell approach with ab initio (AI)-embedded cluster treatments.…”

Section: Introductionmentioning

confidence: 99%

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First-Principles Study of Optical Absorption Energies, Ligand Field and Spin-Hamiltonian Parameters of Cr³⁺ Ions in Emeralds

et al. 2021

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Herein, we study the electronic structure, energies, and vibronic structure of optical d-d transitions of Cr 3+ ions doped in beryl (Be 3 Si 6 Al 2 O 18 :Cr 3+ , 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 Cr 3+ centers in the [CrO 6 ] 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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Section: Computational Protocolmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

First-Principles Study of Optical Absorption Energies, Ligand Field and Spin-Hamiltonian Parameters of Cr³⁺ Ions in Emeralds

et al. 2021

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“…However, in this paper we only analyze the absorption spectrum consisting of transitions from the fundamental state to quartet excited states, allowed by the spin rules. We have carry out all the calculations, based on the methods presented in [24,25], for three valence chromium ion doped in α-Al 2 O 3 :Cr 3+ material using an initial complete active space, consisting of the five-3d metal orbital CAS (3, 5), a good strategy for TM ions doped in host matrices with strongly localized orbitals. The results are collected in tables 1(a) and (b), alongside the experimental data.…”

Section: Resultsmentioning

confidence: 99%

“…Based on the fully relaxed α-Al 2 O 3 :Cr 3+ geometry, the [CrO 6 ] 9− centered embedded cluster, which contains the central Cr 3+ -and six coordinating O 2− ions, according to Gellé -Lepetit procedure [31] was built (for more details the readers are kindly invited to see the papers [24,25]). In this cluster the Cr 3+ ion is coordinated by two groups of oxygen ions, each of them having three oxygen ions, with the new distances Cr 3+ -O 2− of 1.9402 and 1.9893 Å correspondingly, as a result of the optimization process.…”

Section: Methods Of Investigationsmentioning

confidence: 99%

“…The aim of this paper is to investigate, in the unified frame, using the ab initio multireference methodology [24,25], the absorption spectra, ligand field (LF) parameters and g factors for three valence chromium doped α-Al 2 O 3 crystal. The method projects a new view on the connection between the optical and EPR spectra, regarding the local symmetry of the impurity ion, the covalence and the multiconfigurational interactions.…”

Section: Introductionmentioning

confidence: 99%

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Absorption spectra, ligand field parameters and g factors of Cr³⁺ doped α-Al₂O₃ laser crystal: ab initio calculations

Eftimie

Avram

2020

Phys. Scr.

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In this paper we present, in the unified frame, the results of the ab initio investigations of absorption spectra, ligand field parameters and g factors for three valence chromium doped α-Al2O3 crystal. Our calculations are based on a new methodology applied to a cluster [CrO6]9− embedded in an extended point charge field of host matrix ligands. After the differential functional theory optimization of the doped crystal, a vibrational theoretical spectroscopic study based on infrared spectroscopy has been employed in order to confirm the stability of the optimized doped crystal structure. The ab initio energy calculation of the electronic states and corresponding wave functions of Cr3+ are documented from the complete active space self-consistent field. The improved energy states from the N-electron valence second order perturbation theory, second order dynamic correlation dressed complete active space (DCD-CAS2), difference dedicate configuration interaction with three degrees of freedom (MRDDCI3) and spectroscopy-oriented configuration interactions, were analyzed. Based on the ab initio ligand field theory procedure we extracted ligand field parameters and spin–orbit coupling constant which were used to recalculate the energy levels of the studied system. In addition, g factors for the ground state 4A2 of Cr3+ ion in corundum are calculated taking into account the full configuration interaction. The results obtained are discussed and the comparisons with measured values from literature show a reasonable agreement, which justifies and recommend this new route of investigation.

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Low symmetry aspects in electron magnetic resonance (EMR) and optical spectroscopy of coordination compounds of transition ions: Crucial notions and issues, literature survey and database

Rudowicz,

Açıkgöz,

Karbowiak

2024

Coordination Chemistry Reviews

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Optical absorption spectra and g factor of MgO: Mn2+explored by ab initio and semi empirical methods

Cited by 12 publications

References 45 publications

First-Principles Study of Optical Absorption Energies, Ligand Field and Spin-Hamiltonian Parameters of Cr³⁺ Ions in Emeralds

First-Principles Study of Optical Absorption Energies, Ligand Field and Spin-Hamiltonian Parameters of Cr³⁺ Ions in Emeralds

Absorption spectra, ligand field parameters and g factors of Cr³⁺ doped α-Al₂O₃ laser crystal: ab initio calculations

Low symmetry aspects in electron magnetic resonance (EMR) and optical spectroscopy of coordination compounds of transition ions: Crucial notions and issues, literature survey and database

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Optical absorption spectra and g factor of MgO: Mn2+explored by ab initio and semi empirical methods

Cited by 12 publications

References 45 publications

First-Principles Study of Optical Absorption Energies, Ligand Field and Spin-Hamiltonian Parameters of Cr3+ Ions in Emeralds

First-Principles Study of Optical Absorption Energies, Ligand Field and Spin-Hamiltonian Parameters of Cr3+ Ions in Emeralds

Absorption spectra, ligand field parameters and g factors of Cr3+ doped α-Al2O3 laser crystal: ab initio calculations

Low symmetry aspects in electron magnetic resonance (EMR) and optical spectroscopy of coordination compounds of transition ions: Crucial notions and issues, literature survey and database

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First-Principles Study of Optical Absorption Energies, Ligand Field and Spin-Hamiltonian Parameters of Cr³⁺ Ions in Emeralds

First-Principles Study of Optical Absorption Energies, Ligand Field and Spin-Hamiltonian Parameters of Cr³⁺ Ions in Emeralds

Absorption spectra, ligand field parameters and g factors of Cr³⁺ doped α-Al₂O₃ laser crystal: ab initio calculations