Abstract
Synthetic clinopyroxenes along the CaMgSi2O6–CaCoSi2O6 join were investigated by a combined chemical-structural-spectroscopic approach. Single crystals were synthesized by flux growth methods, both from Ca-saturated and Ca-deficient starting compositions. Single crystal structure refinements show that the incorporation of Co2+ at the octahedrally coordinated cation sites of diopside, increases the unit-cell as well as the M1 and the M2 polyhedral volumes. Spectroscopic investigations (UV–VIS–NIR) of the Ca-rich samples reveal three main optical absorption bands, i.e. 4 T 1g → 4 T 2g(F), 4 T 1g → 4 A 2g(F) and 4 T 1g → 4 T 1g(P) as expected for Co2+ at a six-coordinated site. The bands arising from the 4 T 1g → 4 T 2g(F) and the 4 T 1g → 4 T 1g(P) electronic transitions, are each split into two components, due to the distortions of the M1 polyhedron from ideal Oh-symmetry. In spectra of both types, a band in the NIR range at ca 5000 cm−1 is caused by the 4 A 2g → 4 T 1g(F) electronic transition in Co2+ in a cubic field in the M2 site. Furthermore, an additional component to a band system at 14,000 cm−1, due to electronic transitions in Co2+ at the M2 site, is recorded in absorption spectra of Ca-deficient samples. No variations in Dq and Racah B parameters for Co2+ at the M1 site in response to compositional changes, were demonstrated, suggesting complete relaxation of the M1 polyhedron within the CaMgSi2O6–CaCoSi2O6 solid solution.
Similar content being viewed by others
References
Ardit M, Cruciani G, Dondi M (2012) Structural relaxation in tetrahedrally coordinated Co2+ along the gahnite-Co-aluminate spinel solid solution. Am Mineral 97:1394–1401
Ardit M, Dondi M, Cruciani G (2014) On the structural relaxation around Cr3+ along binary solid solutions. Eur J Mineral 26:359–370
Ballhausen CJ, Weiner MA (1963) Introduction to ligand field theory. J Electrochem Soc 110:97C-97C
Bosi F, Hålenius U, D’Ippolito V, Andreozzi GB (2012) Blue spinel crystals in the MgAl2O4–CoAl2O4 series: II. Cation ordering over short range and long range scales. Am Miner 97:1834–1840
Bruno E, Carbonin S, Molin GM (1982) Crystal structure of Ca-rich clinopyroxenes on the CaMgSi2O6-Mg2Si2O6 join. Tscher Mineral Petr Mitt 29:223–240
Burnham CW, Clark JR, Papike JJ, Prewitt CT (1967) A proposed crystallographic nomenclature for clinopyroxene structures. Zeits Krist 125:109–119
Burns RG (1993) Mineralogical applications of crystal field theory. Cambridge University Press
D’Ippolito V, Andreozzi GB, Hålenius U, Skogby H, Hametner K, Günther (2015) Color mechanisms in spinel: cobalt and iron interplay for the blue color. Phys Chem Miner 42:431–439
Dondi M, Zanelli C, Ardit M, Cruciani G (2011) Co-Doped Hardystonite, Ca2(Zn, Co)Si2O7, a New Blue Ceramic Pigment. J Am Ceram Soc 94:1025–1030
Dondi M, Ardit M, Cruciani G, Zanelli C (2014) Tetrahedrally cooordinated Co2+ in oxides and silicates: effect of local environment on optical properties. Am Miner 99:1736–1745
Dou Y (1990) Equations for calculating Dq and B. J Chem Edu 67:134
Farrugia LJ (1999) WinGX suite for small-molecule single-crystal crystallography. J Appl Crystallogr 32:837–838
Ghose S, Wan C, Okamura FP (1987) Crystal structures of CaNiSi2O6 and CaCoSi2O6 and some crystal-chemical relations in C2/c clinopyroxenes. Am Miner 72:375–381
Gori C, Tribaudino M, Mantovani L, Delmonte D, Mezzadri F, Gilioli E, Calestani G (2015) Ca-Zn solid solutions in C2/c pyroxenes: synthesis, crystal structure, and implications for Zn geochemistry. Am Miner 100:2209–2218
Gori C, Tribaudino M, Mantovani L, Gatta GD, Delmonte D, Mezzadri F, Gilioli E, Calestani G (2017) Synthesis and crystal structure of C2/c Ca(Co, Mg)Si2O6 pyroxenes: effect of the cationic substitution on the cell volume. Miner Mag 81:1129–1139
Hugh-Jones DA, Woodland AB, Angel RJ (1994) The structure of high-pressure C2/c ferrosilite and crystal chemistry of high-pressure C2/c pyroxenes. Am Miner 79:1032–1041
Llusar M, Forés A, Badenes JA, Calbo J, Tena MA, Monrós G (2001) Colour analysis of some cobalt-based blue pigments. J Eur Ceram Soc 21:1121–1130
Mantovani L, Tribaudino M, Mezzadri F, Calestani G, Bromiley G (2013) The structure of (Ca,Co)CoSi2O6 pyroxenes and the Ca-M2+ substitution in (Ca,M2+)M2+Si2O6 pyroxenes (M2+= Co, Fe, Mg). Am Mineral 98:1241–1252
Mantovani L, Tribaudino M, Bertoni G, Salviati G, Bromiley G (2014) Solid solutions and phase transitions in (Ca,M2+)M2+Si2O6 pyroxenes (M2+ = Co, Fe, Mg). Am Miner 99:704–711
Mantovani L, Tribaudino M, Dondi M, Zanelli C (2015) Synthesis and color performance of CaCoSi2O6 pyroxene, a new ceramic colorant. Dyes Pigm 120:118–125
Masse S, Boch P, Vaissière N (1999) Trapping of nickel and cobalt in CaNiSi2O6 and CaCoSi2O6 diopside-like phases in heat-treated cement. J Eur Ceram Soc 19:93–98
Momma K, Izumi F (2008) VESTA: a three-dimensional visualization system for electronic and structural analysis. J Appl Crystallogr 41:653–658
Ozel E, Yurdakul H, Turan S, Ardit M, Cruciani G, Dondi M (2010) Co-doped willemite ceramic pigments: Technological behaviour, crystal structure and optical properties. J Eur Ceram Soc 30:3319–3329
Robinson K, Gibbs GV, Ribbe PH (1971) Quadratic elongation: a quantitative measure of distortion in coordination polyhedra. Science 172:567–570
Ross CR, Keppler H, Canil D, O’Neill HSC (1996) Structure and crystal-field spectra of Co3Al2 (SiO4)3 and (Mg, Ni)3Al2 (SiO4) 3 garnet. Am Miner 81:61–66
Rossi G, Oberti R, Dal Negro A, Molin GM, Mellini M (1987) Residual electron density of the M2 site in C2/c clinopyroxenes relationship with bulk chemistry and sub-solidus evolution. Phys Chem Miner 14:514–520
Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr A 32:751–767
Shannon RD, Prewitt CT (1970) Revised values of effective ionic radii. Acta Crystallogr B 26:1046–1048
Sheldrick GM (1996) SADABS, program for empirical absorption correction of area detector data. University of Göttingen, Göttingen
Sheldrick GM (1997) SHELXL-97, program for crystal structure analysis. University of Göttingen, Göttingen
Tabira Y, Ishizawa N, Marumo F (1993) Cobalt atoms at M(2) site in C2/c clinopyroxenes of the system CaMgSi2O6 (Di)–CaCoSi2O6 (CaCoPx). Min J 16:225–245
Tanabe Y, Sugano S (1954) On the absorption spectra of complex ions. I and II. J Phys Soc Jpn 9:753–779
Taran MN, Rossman GR (2001) Optical spectra of Co2+ in three synthetic silicate minerals. Am Mineral 86:889–895
Taran MN, Ohashi H, Koch-Müller M (2008) Optical spectroscopic study of synthetic NaScSi2O6–CaNiSi2O6 pyroxenes at normal and high pressures. Phys Chem Miner 35:117–127
Taran MN, Koch-Müller M, Feenstra A (2009) Optical spectroscopic study of tetrahedrally coordinated Co2+ in natural spinel and staurolite at different temperatures and pressures. Am Mineral 94:1647–1652
Tribaudino M, Ohashi H (2011) High temperature structure and thermal expansion of Co3Al2Si3O12 garnet. Periodico di Mineralogia 80:135–144
Ullrich K, Ott O, Langer K, Becker KD (2004) Temperature dependence of the polarized electronic absorption spectra of olivines. Part II—cobalt-containing olivines. Phys Chem Miner 31:247–260
Underhill AE, Billing DE (1966) Calculations of the racah parameter B for nickel (II) and cobalt (II) compounds. Nature 210:834–835
White BW, McCarthy GJ, Scheetz BE (1971) Optical spectra of chromium, nickel, and cobalt-containing pyroxenes. Am Mineral 56:72–89
Acknowledgements
We thank Michael Taran and an anonymous reviewer for comments that helped to improve the paper.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Gori, C., Tribaudino, M., Mezzadri, F. et al. Co2+-doped diopside: crystal structure and optical properties. Phys Chem Minerals 45, 443–461 (2018). https://doi.org/10.1007/s00269-017-0932-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00269-017-0932-z