What question did this study set out to answer?

To establish accurate numerical parameters for free and covalently bonded divalent manganese ions in octahedral and tetrahedral crystal environments.

October 15, 1974The Journal of Chemical Physics

Covalent bonding of Mn2+ ions in octahedral and tetrahedral coordination

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Authors

DCD. CurieUniversité Claude Bernard Lyon 1 CBCarlos BarthouCentre National de la Recherche Scientifique BCB. CannyInstitut de minéralogie, de physique des matériaux et de cosmochimie

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Implication

Theoretical analysis reveals revised crystal field parameters for divalent manganese complexes, resolving historical spectroscopic discrepancies in luminescent crystals.

Key Points

To establish accurate numerical parameters for free and covalently bonded divalent manganese ions in octahedral and tetrahedral crystal environments.
Evaluated free-ion Racah parameters alongside Racah-Trees and seniority corrections to match experimental quartet energy levels.
Developed a routine trace method using 4E, 4T1, and 4T2 energy matrices to calculate covalent normalization parameters Nt and Ne.
Evaluated the validity of the conventional crystal field parameter Dq formalism using Lohr's intermediate neglect of differential overlap approximation across multiple host crystals.
Identified optimal free-ion parameters of B=960 cm−1 and C=3325 cm−1, achieving exact agreement across all quartet levels only when combining Racah-Trees α and seniority β corrections.
Determined that the conventional Dq formalism remains valid under metal-ligand interactions but fails when ligand-ligand interactions are introduced.
Established the correct crystal field splitting progression Dq(MnBr2) < Dq(MnCl2) < Dq(MnF2), while uncovering an error of up to 6000 cm−1 in prior spectral assignments for MnCl2.

Cite This Study

Curie et al. (1974) studied this question.

synapsesocial.com/papers/6a02f80c98cafe0df5756434 https://doi.org/10.1063/1.1682461

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Implication

Theoretical analysis reveals revised crystal field parameters for divalent manganese complexes, resolving historical spectroscopic discrepancies in luminescent crystals.

Covalent bonding of Mn2+ ions in octahedral and tetrahedral coordination

Discussion

Member takes

Implication

Key Points

Cite This Study

Covalent bonding of Mn2+ ions in octahedral and tetrahedral coordination

Discussion

Member takes

Implication

Key Points

Cite This Study

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