Abstract
Detailed ligand-field spectra of Mn2+ in both microcrystalline and single-crystal synthetic forsterite are obtained using the technique of luminescence excitation spectroscopy.
It is shown that Mn2+ has an almost exclusive preference for one particular cation site which is most probably the M2 site. Low temperature measurements reveal a no-phonon (purely electronic) transition at 16,260 cm−1 (615 nm) which is the energy of the lowest split component of the 4 T 1(G) state above the ground state. Phonon replicas of this transition are evident showing that a particular phonon mode (180 cm−1) is dominantly involved.
An analysis of the polarized spectra of Mn2+ in single-crystal forsterite shows the choice of C 2v (C 2, σ d ) pseudosymmetry for the M2 site yields the best agreement with the polarization dependence of the transitions between the ligand-field states of the Mn2+ ion in this site.
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References
Bragg WL, Brown GB (1926) Die Struktur des Olivins. Z Kristallogr 63:538–556
Burns RG (1970a) Crystal field spectra and evidence of cation ordering in olivine minerals. Am Mineral 55:1608–1632
Burns RG (1970b) Mineralogical applications of crystal field theory. Cambridge University Press, Cambridge, England
Chatelain A, Weeks RA (1970) Electron paramagnetic resonance study of ordered Mn2+ in Mg2SiO4. J Chem Phys 52:5682–5687
Cotton FA (1971) Chemical applications of group theory (2nd ed). Wiley-Interscience
Fleet ME (1974) Distortions in coordination polyhedra of M-site atoms in olivines, pyroxenes and amphiboles. Am Mineral 59:1083–1093
Finch CB, Clark GW (1971) Czochralski growth of single crystal Mg2SiO4 (forsterite). J Cryst Growth 8:307–308
Gaite JM (1975) EPR study of Mn2+ in diopside. J Phys C (Solid State Phys) 8:3887–3895
Geake JE, Walker G, Mills AA, Garlick GFJ (1972) Luminescence of lunar material excited by electrons. Proceedings of the Third Lunar Science Conference. Suppl 3, Geochim et Cosmochim Acta 3:2971–2979
Green GR (1981) Spectroscopic studies of transition-metal luminescence centres in silicates. PhD thesis, University of Manchester
Hamilton D, Henderson CMB (1968) Preparation of silicate minerals by a gelling method. Mineral Mag 36:(382) 832–838
Hamilton TDS, Munro IH, Walker G (1978) Luminescence Instrumentation, in MD Lumb, Ed, Luminescence Spectroscopy. Academic Press, London and New York, pp 149–238
Hawthorne FC (1983) Quantitative characterization of site occupancies in minerals. Am Mineral 68:287–306
Hazen RM (1976) Effects of temperature and pressure on the crystal structure of forsterite. Am Mineral 61:1280–1293
Huggins FE (1973) Cation order in olivines: evidence from vibrational spectra. Chem Geol 11:99–109
Iishi K (1978) Lattice dynamics of forsterite. Am Mineral 63:1198–1208
Imbusch GF (1978) Inorganic Luminescence. In MD Lumb (Ed), Luminescence Spectroscopy. Academic Press, London and New York, pp 1–92
Mehra A, Venkateswarlu P (1967) Absorption spectrum of RbMnF3. J Chem Phys 47:2334–2342
Michoulier J, Gaite JM, Maffeo B (1969) Résonance paramagnétique électronique de l'ion Mn2+ dans un monocristal de forsterite. Compt Rend Acad Sci Paris 269B:535–538
Oehler O, Gunthard HH (1969) Low-temperature infrared spectra between 1,200 and 20 cm−1 and normal coordinate analysis of silicates with olivine structure. J Chem Phys 51:4719–4728
Rager H (1980) Electric field gradients and asymmetry parameters of Fe3+, Mn2+, Cr3+, and Mg2+ in Mg2SiO4. J Mol Structure 58:215–220
Rager H, Weiser G (1981) Polarized absorption spectra of trivalent chromium in forsterite, Mg2SiO4. Bull Mineralogie 104:603–609
Rager H, Hosoya S (1984) Site symmetries in olivines obtained from structural and spectroscopic data. Collected Abstracts, 13th International Congress of Crystallography, Hamburg
Runciman WA, Sengupta D, Gourley JT (1973) The polarized spectra of iron in silicates, II Olivine. Am Mineral 58:451–456
Servoin JL, Piriou B (1973) Infrared reflectivity and Raman scattering of Mg2SiO4 single crystal. Phys Status Solidi (b) 55:677–686
Smyth JR, Hazen RM (1973) The crystal structures of forsterite and hortonolite at several temperatures up to 900° C. Am Mineral 58:588–593
Telfer DJ, Walker G (1975) Optical detection of Fe3+ in lunar plagioclase. Nature (London) 258:694–695
Telfer DJ, Walker G (1978) Ligand field bands of Mn2+ and Fe3+ luminescence centres and their site occupancy in plagioclase feldspars. Mod Geol 6:199–210
Walker G (1983) Luminescence centres in minerals. Chem Britain 19:824–831
Walker G (1985) Mineralogical applications of luminescence techniques. In: Berry FJ, Vaughan DJ (Ed) Chemical Bonding and Spectroscopy in Mineral Chemistry. Chapman and Hall, London, pp 103–140
Weeks RA, Pig JC, Finch CB, (1974) Charge transfer spectra of Fe3+ and Mn2+ in synthetic forsterite. Am Mineral 59:1259–1266
Wilson EB, Decius SC, Cross PC (1955) Molecular vibrations. McGraw-Hill, New York
Wood BJ (1974) Crystal field spectra of Ni2+ in olivine. Am Mineral 59:244–248
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Green, G.R., Walker, G. Luminescence excitation spectra of Mn2+ in synthetic forsterite. Phys Chem Minerals 12, 271–278 (1985). https://doi.org/10.1007/BF00310339
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DOI: https://doi.org/10.1007/BF00310339