Covalent bonding of Mn2+ ions in octahedral and tetrahedral coordination

This paper is divided into four parts: The first part (Sec. I) contains a brief review of different assumptions made by several authors for the numerical values of the free Mn2+ ion parameters. It is shown that if only the Racah parameters B and C are taken into account, then the Orgel‐Griffith choice B=960 cm−1, C=3325 cm−1 seems to be the best one. Tanabe and Sugano's figures lead to errors as high as 3800 cm−1. Adding only the Racah‐Trees correction α does not seriously improve the fitting of levels 4G, 4D, and 4F because a singular set of equations is then obtained. An exact experimental agreement can be obtained for all quartet levels by simultaneously using the Racah‐Trees correction α and the seniority correction β. The best fit values of the adjustable parameters relevant to the Mn2+ ion are given; it is found that α and β do not differ very much from Shadni's values. Section II deals with the well‐known use of the two normalization parameters Nt, Ne for describing covalent bonding. A routine meth...

[1]  T. Kushida,et al.  Excited-state absorption spectra of ZnS : Mn , 1974 .

[2]  B. Lambert,et al.  Optical Properties ofMn2+in Pure and Faulted Cubic ZnS Single Crystals , 1973 .

[3]  S. Freeman.  Molecular-Orbital Theory of the Excited-State Exchange Interaction , 1973 .

[4]  C. Blanchard,et al.  Effect of the second order spin orbit and spin-spin interactions on the 4E (G) level of Mn2+ in ZnS , 1972 .

[5]  R. Dingle,et al.  Tetrahedral transition-metal complex spectra. Optical spectra of tetrahalo-manganates (II) , 1972 .

[6]  D. T. Palumbo,et al.  Electronic States of Mn2+‐Activated Phosphors II . Orange‐to‐Red Emitting Phosphors , 1971 .

[7]  L. L. Lohr.  Radial Expansion of 3d Orbitals and the Near Degeneracy of the 4A1g and 4Eg Excited States of Octahedral Mn(II) Complexes , 1971 .

[8]  J. Richardson,et al.  Electronic Structure and Spectrum of the NiF6-4 Cluster: Results of Calculations Based on Self-Consistent-Field Models , 1971 .

[9]  A. Mehra.  Energy Levels of Divalent Manganese in ZnS , 1971 .

[10]  C. Jørgensen.  Modern aspects of ligand field theory , 1971 .

[11]  D. T. Palumbo,et al.  Electronic States of Mn2+‐Activated Phosphors. I . Green‐Emitting Phosphors , 1970 .

[12]  J. Richardson,et al.  Electron Delocalization and the Neutron Magnetic Form Factor ofMn+2andNi+2Antiferromagnetic Salts , 1970 .

[13]  A. Freeman,et al.  Covalent bonding and the neutron magnetic form factor of the Mn2+ Ion , 1970 .

[14]  F. Tsay,et al.  Covalent Bonding in Octahedral (MnCl6)4− and Tetrahedral (MnCl4)2− Complexes , 1969 .

[15]  A. Mehra.  Optical Absorption of Mn2+-Doped Alkali Halides , 1968 .

[16]  D. S. Falk,et al.  Phonons: In Perfect Lattices and in Lattices with Point Imperfections , 1967 .

[17]  L. L. Lohr.  Optical Spectra of Divalent Manganese Salts. I. Energy Levels for Cubic and Lower‐Symmetry Complexes , 1966 .

[18]  K. E. Lawson.  Electronic Absorption Spectra of Mn2+, Fe2+, and Co2+ in Dihydrated Halide Crystals , 1966 .

[19]  R. Stevenson.  Phonons in perfect lattices and in lattices with point imperfections : Scottish Universities' Summer School, 1965 , 1966 .

[20]  Hiroshi Watanabe.  Operator methods in ligand field theory , 1966 .

[21]  Y. Shadmi.  Interaction between 3 d and 3 s Electrons in the Second Spectra of the Iron Group , 1965 .

[22]  D. Langer,et al.  Zero-Phonon Lines and Phonon Coupling in ZnS:Mn , 1965 .

[23]  D. McClure,et al.  Optical Spectra of Exchange Coupled Mn ++ Ion Pairs in ZnS:MnS , 1963 .

[24]  R. Shulman,et al.  Covalency Effects in KNiF3. I. Nuclear Magnetic Resonance Studies , 1963 .

[25]  F. Cotton,et al.  Absorption Spectra and Electronic Structures of Some Tetrahedral Manganese(II) Complexes , 1962 .

[26]  J. Griffith,et al.  The Theory of Transition-Metal Ions , 1962 .

[27]  C. Jørgensen,et al.  Parameters α and β in the Spectra of the Iron Group , 1961 .

[28]  R. Pappalardo.  Note on the Optical Absorption of MnCl2 and MnBr2 , 1960 .

[29]  J. W. Stout.  Absorption Spectra of MnCl2 and MnBr2 , 1960 .

[30]  J. W. Stout.  Absorption Spectrum of Manganous Fluoride , 1959 .

[31]  M. Pryce,et al.  Intensity Calculation of Some Optical Absorption Lines in Hydrated Manganous Salts , 1958 .

[32]  G. Racah.  L(L+1)Correction in the Spectra of the Iron Group , 1952 .

[33]  R. E. Trees.  TheL(L+1)Correction to the Slater Formulas for the Energy Levels , 1952 .