Raman spectroscopy of CaCoSi2O6–Co2Si2O6 clinopyroxenes

Mantovani, Luciana; Tribaudino, Mario; Aliatis, Irene; Lambruschi, Erica; Lottici, Pier Paolo; Bersani, Danilo

doi:10.1007/s00269-014-0707-8

Cited by 13 publications

(17 citation statements)

References 31 publications

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“…Twenty‐two peaks at most were identified in the range 90–900 cm −1 . To our best knowledge, no assignment of the Raman bands of germanate pyroxenes has been yet carried out, but many studies exist about silicate pyroxenes . Recently, ab initio quantum mechanical calculations of Raman and IR wavenumbers and intensities were published.…”

Section: Resultsmentioning

confidence: 99%

“…The small variations in the tetrahedral bond lengths cannot explain this behavior, and an effect of the mass of the M1 cation could hardly be invoked. Actually, in the Co and Mg pyroxenes, the T‐O stretching mode occurs at the same wavenumber (1012 cm −1 ), in spite of the significant M1 mass difference. Preliminary quantum mechanical simulations show indeed poorer agreement between experiment and calculations for this high wavenumber mode in germanates with respect to silicates.…”

Section: Resultsmentioning

confidence: 99%

“…Two silicate samples were investigated for comparison: natural diopside CaMgSi 2 O 6 and synthetic cobalt pyroxene CaCoSi 2 O 6 …”

Section: Methodsmentioning

confidence: 99%

“…Wide chemical substitutions may occur within each site: Ca, Mg, Fe, Na, Mn, Ni, Li, Zn, Mg, and Fe 2+ for M2, Mg, Fe 2+ , Fe 3+ , Ti, In, Sc, Al, Ga, Mn, Co, Ni, Zn for M1, and Si, Al, and Ge for T . Therefore, pyroxenes are well suited to test the effect of chemical substitution in a relatively simple structure: the extent and the effect of changes in cation radii, site occupancy, and crystal field stabilization can be experimentally monitored …”

Section: Introductionmentioning

confidence: 99%

“…Other symmetries are present but rarely found in natural or synthetic pyroxenes . Extended Raman studies were performed on clinopyroxenes, with the aim of using them as a probe for further geological investigation, but also to clarify the relations between vibration modes and structure . As in natural clinopyroxenes, the tetrahedral cation is invariably Si, with a small Al substitution, if any, Raman studies were almost completely devoted to clinopyroxenes with Si in the tetrahedral site.…”

Section: Introductionmentioning

confidence: 99%

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Raman spectroscopy of CaM²⁺Ge₂O₆(M²⁺ = Mg, Mn, Fe, Co, Ni, Zn) clinopyroxenes

Lambruschi

Aliatis

Mantovani

et al. 2015

J. Raman Spectrosc.

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The Raman spectra of Ge‐clinopyroxenes CaM2+Ge2O6 (M2+ = Mg, Mn, Fe, Co, Ni, Zn), general formula M2M1T2O6, are reported for the first time. Their spectral features are discussed in comparison with corresponding Si‐pyroxenes. The vibrational wavenumbers of germanates may be roughly obtained by a scale factor of about ~0.8 by those of the corresponding silicates, due to the Ge‐Si mass difference. The main peaks in the germanate Raman spectra at ~850 and ~540 cm−1 may be related to Ge‐O tetrahedral stretching and chain bending, respectively; minor peaks between 200 and 400 cm−1 are ascribed to bending and stretching of the non‐tetrahedral cations. Within Ge‐pyroxenes, possible correlations between crystallographic parameters and the vibrational wavenumbers are investigated. The main stretching mode at ~850 cm−1 shows wavenumber changes with M2+ substitutions, but no simple correlation can be found with M2+ cation mass or size. On the other hand, the chain bending wavenumber linearly decreases with increasing ionic radius of the M2+ cation: the expansion of the M1 polyhedron reduces the chain kinking angle and the Ge‐Ge distances correspondingly increase. Copyright © 2015 John Wiley & Sons, Ltd.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…Two silicate samples were investigated for comparison: natural diopside CaMgSi 2 O 6 and synthetic cobalt pyroxene CaCoSi 2 O 6 …”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Raman spectroscopy of CaM²⁺Ge₂O₆(M²⁺ = Mg, Mn, Fe, Co, Ni, Zn) clinopyroxenes

Lambruschi

Aliatis

Mantovani

et al. 2015

J. Raman Spectrosc.

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Raman modes inPbcaenstatite (Mg₂Si₂O₆): an assignment by quantum mechanical calculation to interpret experimental results

Stangarone

Tribaudino

Prencipe

et al. 2016

J. Raman Spectrosc.

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Raman spectra of orthoenstatite have been computed from first principles, employing the hybrid Hamiltonian WC1LYP. The calculated data show excellent agreement with the experimental data from literature with an absolute average difference of ~5 cm−1. The quantum mechanical simulation allowed the assignment of Raman features to specific vibrational modes. This enabled to assess quantitatively the contributions of internal (tetrahedral stretching) and external (tetrahedral chains and M1 and M2 cations) vibrations. Moreover, the mass substitution of 56Fe for 24Mg in the M1 and M2 sites and of 30Si and 18O for the 28Si and 16O sites, pointed out the relative contributions of the cations to each mode within different sites. The description of the Raman modes enabled to relate the major experimental peaks to specific structural vibrations, and to link the changes in crystal structure to those modes with pressure, temperature and composition. The results provide new clues to identify most suitable peaks for the investigation of the intracrystalline ordering of Fe and Mg in the M1 and M2 sites, and of Al in the tetrahedral and octahedral sites. Moreover we have been able to identify those peaks which are related to structural features, like tetrahedral bond distances. Copyright © 2016 John Wiley & Sons, Ltd.

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High‐pressure Raman spectroscopy of Ca(Mg,Co)Si₂O₆ and Ca(Mg,Co)Ge₂O₆ clinopyroxenes

Tribaudino

Aliatis

Bersani

et al. 2017

J Raman Spectroscopy

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In situ high‐pressure Raman spectra were collected on four pyroxenes, with composition CaCoSi2O6, CaMgSi2O6, CaCoGe2O6 and CaMgGe2O6, up to P = 7.6 and 8.3 GPa for silicates and germanates, respectively. The peak wavenumbers υi increase almost linearly with pressure; the slope dυi/dP is more pronounced for the modes at higher wavenumbers, and higher in germanates than in silicates. No phase transition or change in the compressional behaviour was observed within the investigated P‐range. The strong dependence of the peak position with pressure of the high energy stretching modes is due to the high sensitivity of the vibrational frequencies probed by Raman spectroscopy to subtle changes in the tetrahedral deformation, which are overlooked by single‐crystal X‐ray diffraction. Copyright © 2017 John Wiley & Sons, Ltd.

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Raman spectroscopy of CaCoSi2O6–Co2Si2O6 clinopyroxenes

Abstract: configurations which affect the short range interactions and therefore the Raman frequencies.

Cited by 13 publications

References 31 publications

Raman spectroscopy of CaM²⁺Ge₂O₆(M²⁺ = Mg, Mn, Fe, Co, Ni, Zn) clinopyroxenes

Raman spectroscopy of CaM²⁺Ge₂O₆(M²⁺ = Mg, Mn, Fe, Co, Ni, Zn) clinopyroxenes

Raman modes inPbcaenstatite (Mg₂Si₂O₆): an assignment by quantum mechanical calculation to interpret experimental results

High‐pressure Raman spectroscopy of Ca(Mg,Co)Si₂O₆ and Ca(Mg,Co)Ge₂O₆ clinopyroxenes

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Raman spectroscopy of CaCoSi2O6–Co2Si2O6 clinopyroxenes

Abstract: configurations which affect the short range interactions and therefore the Raman frequencies.

Cited by 13 publications

References 31 publications

Raman spectroscopy of CaM2+Ge2O6(M2+ = Mg, Mn, Fe, Co, Ni, Zn) clinopyroxenes

Raman spectroscopy of CaM2+Ge2O6(M2+ = Mg, Mn, Fe, Co, Ni, Zn) clinopyroxenes

Raman modes inPbcaenstatite (Mg2Si2O6): an assignment by quantum mechanical calculation to interpret experimental results

High‐pressure Raman spectroscopy of Ca(Mg,Co)Si2O6 and Ca(Mg,Co)Ge2O6 clinopyroxenes

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Product

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Raman spectroscopy of CaM²⁺Ge₂O₆(M²⁺ = Mg, Mn, Fe, Co, Ni, Zn) clinopyroxenes

Raman spectroscopy of CaM²⁺Ge₂O₆(M²⁺ = Mg, Mn, Fe, Co, Ni, Zn) clinopyroxenes

Raman modes inPbcaenstatite (Mg₂Si₂O₆): an assignment by quantum mechanical calculation to interpret experimental results

High‐pressure Raman spectroscopy of Ca(Mg,Co)Si₂O₆ and Ca(Mg,Co)Ge₂O₆ clinopyroxenes