SpringerLink
Log in

Single-crystal absorption and reflection infrared spectroscopy of forsterite and fayalite

  • Published:
Physics and Chemistry of Minerals Aims and scope Submit manuscript

Abstract

Polarized single-crystal absorption and reflection spectra of fundamental modes in both the mid- and far-infrared are presented for microscopic crystals of forsterite and fayalite. All modes predicted by symmetry were observed for forsterite, but two B3u modes were not observed for fayalite. Consideration of previously determined frequency shifts for isotopically and chemically substituted olivines, along with symmetry analysis, produced a complete set of band assignments satisfying all constraints for forsterite. A plausible assingment was derived for fayalite by analogy. The frequency shifts from forsterite to fayalite are consistently small for bands assigned to SiO4 stretching and bending, moderate for rotations, and large for translations of M-site ions, suggesting that in olivine, SiO4 groups vibrate separately from the lattice. Allocating the bending and external modes among multiple continua in Kieffer's (1979c) model considerably improves prediction of quasiharmonic heat capacityC v and entropy for forsterite (∼1% discrepancy from 200–1000 K). The experimental entropy of fayalite is closely accounted for (1.8 to 0.1%) by summing lattice, electronic (from Burns' (1985) optical band assignment), and constant magnetic contributions above 200 K.S magnetic determined from the difference of the experimental and model lattice entropies shows inflection points at the two magnetic transition temperatures (23 and 66 K) and indicates that complete spin disorder is not achieved below 680 K.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • Akaogi M, Ross NL, McMillan P, Navrotsky A (1984) The Mg2SiO4 polymorphs (olivine, modified spinel and spinel)-thermodynamic properties from oxide melt solution calorimetry, phase relations, and models of lattice vibrations. Am Mineral 69:499–512

    Google Scholar 

  • Berman RG, Brown TH (1985) Heat capacity of minerals in the system Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-SiO2-TiO2-H2O-CO2: representation, estimation, and high temperature extrapolation. Contrib Mineral Petrol 89:168–183

    Google Scholar 

  • Berreman DW (1963) Infrared absorption at longitudinal optic frequency in cubic crystal films. Phys Rev 130:2193–2198

    Google Scholar 

  • Burns RG (1985) Thermodynamic data from crystal field spectra. Microscopic to macroscopic — atomic environments to mineral thermodynamics. Revs Mineral 14:277–316

    Google Scholar 

  • Burns RG, Huggins FE (1972) Cation determination curves for Mg-Fe-Mn olivines from vibrational spectra. Am Mineral 57:967–985

    Google Scholar 

  • Duke DA, Stephens JD (1964) Infrared investigation of the olivine group mineral. Am Mineral 49:1388–1406

    Google Scholar 

  • Farmer VC, Lazarev AN (1974) Symmetry and crystal vibrations. In: Farmer VC (ed) The infrared spectra of minerals. Mineralogical Society, London, pp 51–68

    Google Scholar 

  • Fately WG, McDevitt NT, Bently FF (1971) Infrared and Raman selection rules for lattice vibrations: The correlation method. Appl Spectros 25:155–174

    Google Scholar 

  • Finch CB, Clark GW, Kopp OC (1980) Czochralski growth of single-crystal fayalite under controlled oxygen fugacity conditions. Am Mineral 65:381–389

    Google Scholar 

  • Graham EK Jr, Barsch GR (1969) Elastic constants of single-crystal forsterite as a function of temperature and pressure. J Geophys Res 74:5949–5960

    Google Scholar 

  • Griffith WP (1969) Raman studies on rock-forming minerals. Part 1. Orthosilicates and cyclosilicates. J Chem Soc A:1372–1377

    Google Scholar 

  • Hazen RM (1976) Effects of temperature and pressure on the crystal structure of forsterite. Am Mineral 61:1280–1293

    Google Scholar 

  • Hazen RM, Finger LW (1982) Comparative crystal chemistry: temperature, pressure, composition, and the variation of crystal structure. John Wiley and Sons, New York

    Google Scholar 

  • Hofmeister AM, Hoering TC, Virgo D (1987) Vibrational spectroscopy of beryllium aluminosilicates: heat capacity calculations from band assignments. Phys Chem Mineral 14:205–224

    Google Scholar 

  • Hofmeister AM, Xu J, Akimoto S (1986) Thermodynamic implication of infrared spectroscopy of stishovite at mantle pressures. Int Mineral Assoc Abstr Progr 14:126

    Google Scholar 

  • Iishi K (1978) Lattice dynamics of forsterite. Am Mineral 63:1198–1208

    Google Scholar 

  • Kieffer SW (1979a) Thermodynamics and lattice vibrations of minerals: 1. Mineral heat capacities and their relationships to simple lattice vibrational models. Rev Geophys Space Phys 17:1–19

    Google Scholar 

  • Kieffer SW (1979b) Thermodynamics and lattice vibrations of minerals: 2. Vibrational characteristics of silicates. Rev Geophys Space Phys 17:20–34

    Google Scholar 

  • Kieffer SW (1979c) Thermodynamics and lattice vibration of minerals: 3. Lattice dynamics and an approximation for minerals with application to simple substances and framework silicates. Rev Geophys Space Phys 17:35–59

    Google Scholar 

  • Kieffer SW (1980) Thermodynamics and lattice vibrations of minerals: 4. Application to chain and sheet silicates and orthosilicates. Rev Geophys Space Phys 18:862–886

    Google Scholar 

  • Kovach JJ, Hiser AL, Karr C Jr (1975) Far-infrared spectroscopy of minerals. In: Karr C Jr (ed) Infrared and Raman spectroscopy of lunar and terrestrial mineral. Academic Press, New York, pp 231–254

    Google Scholar 

  • Kundig W, Cape JA, Lindquist RH, Constabaris G (1967) Some magnetic properties of Fe2SiO4 from 4 K to 300 K. J Appl Phys 38:947–948

    Google Scholar 

  • Moller KD, Rothschild WG (1970) Fr-infrared spectroscopy. Wiley-Interscience, New York, pp 303–324

    Google Scholar 

  • Nakamoto K (1978) Infrared and Raman spectra of inorganic and coordination compounds. John Wiley and Sons, New York, pp 140–146

    Google Scholar 

  • Oehler O, Gunthard HsH (1969) Low-temperature infrared spectra between 1200 and 20 cm−1 and normal-corrdinate analysis of silicates with olivine structure. J Chem Phys 51:4719–4728

    Google Scholar 

  • Paques-Ledent MTh, Tarte P (1973) Vibrational studies of olivine-type compounds I. The IR and Raman spectra of the isotopic species of Mg2SiO4. Spectrochim Acta 29A:1007–1016

    Google Scholar 

  • Robie RA, Finch CB, Hemingway BS (1982a) Heat capacity and entropy of fayalite (Fe2SiO4) between 5.1 and 383 K: comparison of calorimetric and equilibrium values for the QFM buffer reaction. Am Mineral 67:436–469

    Google Scholar 

  • Robie RA, Hemingway BS, Takei M (1982b) Heat capacities and entropies of Mg2SiO4, Mn2SiO4, and Co2SiO4 between 5 and 380 K. Am Mineral 67:470–482

    Google Scholar 

  • Servoin JL, Piriou B (1973) Infrared reflectivity and Raman scattering of Mg2SiO4 single crystal. Phys Status Solidi B55:677–686

    Google Scholar 

  • Sharp ZD, Essene EJ, Anovitz LM, Metz GW, Westrum EF Jr, Hemingway BS, Valley JW (1986) The heat capacity of a natural monticellite and phase equilibria in the system CaO-MgO-SiO2-CO2. Geochim Cosmochim Acta 50:1475–1484

    Google Scholar 

  • Smyth JR Jr (1975) High temperature crystal chemistry of fayalite. Am Mineral 60:1092–1097

    Google Scholar 

  • Suzuki I, Seya K, Takei H, Sumino Y (1981) Thermal expansion of fayalite, Fe2SiO4. Phys Chem Minerals 7:60–63

    Google Scholar 

  • Ulbrich HH, Waldbaum DR (1976) Structural and other contributions to the third-law entropies of silicates. Geochim Cosmochim Acta 40:1–24

    Google Scholar 

  • Watanabe H (1982) Thermochemical properties of synthetic high-pressure compounds relevant to the earth's mantle. In: Akimoto S, Manghnani MH (eds) High pressure research in geophysics. Center for Academic Publications. Tokyo, pp 441–464

    Google Scholar 

  • White GK, Roberts RB, Collins JG (1985) Thermal properties and Gruneisen functions of forsterite, Mg2SiO4. High Temp High Pressures 17:61–66

    Google Scholar 

  • Wood BJ (1981) Crystal field electronic effects on the thermodynamic properties of Fe2+ minerals. In: Newton RC, Navrotsky A, Wood BJ (eds) Thermodynamics of minerals and melts. Springer-Verlag, New York, pp 63–84

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Geophysical Laboratory, Carnegie Institution of Washington, 2801 Upton St., N.W., 20008, Washington, D.C., USA

    Anne M. Hofmeister

Authors
  1. Anne M. Hofmeister
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Hofmeister, A.M. Single-crystal absorption and reflection infrared spectroscopy of forsterite and fayalite. Phys Chem Minerals 14, 499–513 (1987). https://doi.org/10.1007/BF00308285

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00308285

Keywords

Search

Navigation