Physics and Chemistry of Minerals

, Volume 34, Issue 5, pp 319–333 | Cite as

Evidence for kinks in structural and thermodynamic properties across the forsterite–fayalite binary from thin-film IR absorption spectra

  • A. M. HofmeisterEmail author
  • K. M. Pitman
Original Paper


Infrared absorbance spectra over ∼100 to 1,800 cm−1 were collected from optically thin films of 21 samples with compositions spanning the forsterite–fayalite binary. Polarization information from previous specular reflectance data on end-members was used in tracing the peaks across the entire binary. Peak positions (νi) were constrained by Lorentzian decompositions. Fitting also constrained widths for singlet peaks but for doublets and triplets, variation in νi with composition among the constituent polarizations alters widths from intrinsic. Because film thicknesses of 0.6–1.4 μm were estimated, our band strengths are approximate; however, relative intensities should be correct. Only for a few peaks does νi vary smoothly across the entire binary; instead, distinct linear trends exist for Fe- and Mg-rich olivines. Discontinuities and kinks in νi(X) occur at X = Mg/(Fe + Mg) = 0.7 and are accompanied by a change in intensity patterns. This interesting behavior was not revealed in previous spectra of powder dispersions. The contrasting character of IR vibrations for Fe- and Mg-rich olivines is inferred to arise from structural variations because (1) frequency is related to bond length, (2) other factors affecting frequency (cation mass and probably bonding type) vary linearly across the binary, and (3) available data on unit cell parameters are consistent with distinct trends for forsterites and fayalites. Vibrational components of heat capacity (C V) and enthalpy (H) calculated from νi, were found to be slightly more negative than linear interpolations between values for forsterite and fayalite. Our computations give smaller negative excesses from ideality in H than do previous calorimetric measurements, but are equal within experimental uncertainties.


Olivine Infrared Solid solution Thermodynamics Structure 



This work was supported by NASA APRA04-000-0041. The authors thank E. Keppel for her help in collecting IR spectra. Special thanks are due to R.M. Hazen, S.A. Morse, and H.S. Yoder for providing most of the olivines used in this study. Samples were also kindly provided by C.B. Finch, B. Fegley, K. Francis, C. Koike, and H.K. Mao. We thank D. Kremser and M. Pertermann for providing microprobe analyses. Critical comments by S. Nakashima led to substantial improvements of the manuscript.


  1. 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 69:499–512Google Scholar
  2. Armstrong JT (1988) Bence-Albee after 20 years: review of the accuracy of α-factor correction procedures for oxide and silicate minerals. In: Newbury DE (ed) Microbeam analysis. San Francisco Press Inc., San Francisco, pp 469–476Google Scholar
  3. Batsanov SS, Derbeneva SS (1969) Effect of valency and coordination of atoms on position and form of infrared absorption bands in inorganic compounds. J Struct Chem (USSR) 10:510–515CrossRefGoogle Scholar
  4. Berreman RG (1963) Infrared absorption at longitudinal optic frequency in cubic crystal films. Phys Rev 130:2193–2198CrossRefGoogle Scholar
  5. Bowen NL, Schairer JF, Posnjak E (1933) The system Ca2SiO4–Fe2SiO4. Am J Sci 26:233–297CrossRefGoogle Scholar
  6. Burns RG (1985) Thermodynamic data from crystal field spectra. Microscopic to macroscopic—atomic environments to mineral thermodynamics. Rev Min 14:277–316Google Scholar
  7. Burns G (1990) Solid state physics. Academic, San DiegoGoogle Scholar
  8. Burns P, Hawthorne FC, Hofmeister AM, Moret SL (1996) A ferroelastic phase transition in K(Mg1−xCux)F3 perovskite. Phys Chem Mineral 23:141–150Google Scholar
  9. Chang IF, Mitra SS (1968) Application of a modified random-element-isodisplacement model to long-wavelength optic phonons of mixed crystals. Phys Rev 172:924–933CrossRefGoogle Scholar
  10. Fabian D, Henning T, Jäger C, Mutschke H, Dorschner J, Wehrban O (2001) Steps toward interstellar silicate mineralogy VI. Dependence of crystalline olivine IR spectra on iron content and particle shape. Astron Astrophys 378:228–238CrossRefGoogle Scholar
  11. Fateley WG, McDevitt NT, Bently FF (1971) Infrared and Raman selection rules for lattice vibrations: the correlation method. Appl Spectrosc 25:155–174CrossRefGoogle Scholar
  12. Fei Y (1995) Thermal expansion. In: Ahrens TJ (ed) A handbook of physical constants. American Geophysical Union, Washington, pp 29–44Google Scholar
  13. Finch CB, Clark GW, Koop OC (1980) Czochralski growth of single-crystal fayalite under controlled oxygen fugacity conditions. Am Mineral 65:381–389Google Scholar
  14. Hirschmann M (1991) Thermodynamics of multicomponent olivines and the solution properties of (Ni,Mg,Fe)2SiO4 and (Ca,Mg,Fe)2SiO4 olivines. Am Mineral 76:1232–1248Google Scholar
  15. Hofmeister AM (1987) Single-crystal absorption and reflection infrared spectroscopy of forsterite and fayalite. Phys Chem Mineral 14:499–513CrossRefGoogle Scholar
  16. Hofmeister AM (1993) IR reflectance spectra of natural ilmenite: comparison with isostructural compounds and calculation of thermodynamic properties. Eur J Mineral 5:281–295Google Scholar
  17. Hofmeister AM (1997) Infrared reflectance spectra of fayalite, and absorption data from assorted olivines, including pressure and isotope effects. Phys Chem Mineral 24:535–546CrossRefGoogle Scholar
  18. Hofmeister AM (2004) Thermal conductivity and thermodynamic properties from infrared spectroscopy. In: King P, Ramsey M, Swayze G (eds) Infrared spectroscopy in geochemistry, exploration geochemistry, and remote sensing. Mineralogical Association of Canada, Ottawa, pp 135–154Google Scholar
  19. Hofmeister AM, Bowey JE (2006) Quantitative IR spectra of hydrosilicates and related minerals. Mon Not R Astron Soc 367:577–591CrossRefGoogle Scholar
  20. Hofmeister AM, Mao HK (2001) Evaluation of shear moduli and other properties of silicates with the spinel structure form IR spectroscopy. Am Mineral 86:622–639Google Scholar
  21. Hofmeister AM, Xu J, Mao H-K, Bell PM, Hoering TC (1989) Thermodynamics of Fe–Mg olivines at mantle pressures: mid- and far-infrared spectroscopy at high pressure. Am Mineral 74:281–306Google Scholar
  22. Hofmeister AM, Rosen L, Speck AK, Barlow MJ (2000) Infrared spectra of nanocrystals of SiC, AlN and TiN: implications for scattering theory. In: Sitko M, Sprague AL, Lynch DK (eds) Thermal emissions spectroscopy and analysis of dust, disks and regoliths. ASP conference series, vol 196, pp 292–300Google Scholar
  23. Hofmeister AM, Keppel E, Speck AK (2003) Absorption and reflection IR spectra of MgO and other diatomic compounds. Mon Not R Astron Soc 345:16–38CrossRefGoogle Scholar
  24. Horak M, Vitek A (1978) Interpretation and processing of vibrational spectra. Wiley, New YorkGoogle Scholar
  25. Huang E, Xu J-A, Chen CH, Huang T, Lin EH (2000) Raman spectroscopic characteristics of Mg–Fe–Ca pyroxenes. Am Mineral 85:473–479Google Scholar
  26. Iishi K (1978) Lattice dynamics of forsterite. Am Mineral 63:1198–1208Google Scholar
  27. Kieffer SW (1979) Thermodynamics and lattice vibrations of mineral: 3. Lattice dynamics and an approximation for minerals with application to simple substances and framework silicates. Rev Geophys Space Phys 17:35–39Google Scholar
  28. Koike C, Chihara H, Tsuchiyama A, Suto H, Sogawa H, Okuda H (2003) Compositional dependence of infrared absorption spectra of crystalline silicate. II. Natural and synthetic olivines. Astron Astrophys 389:1101–1107CrossRefGoogle Scholar
  29. Kojitani H, Akoagi M (1994) Calorimetric study of olivine solid solutions in the system Mg2SiO4–Fe2SiO4. Phys Chem Mineral 20:536–540CrossRefGoogle Scholar
  30. Mitra SS (1969) Infrared and Raman spectra due to lattice vibrations. In: Nudelman S, Mitra SS (eds) Optical properties of solids. Plenum, New York, pp 333–452Google Scholar
  31. Morse SA (1996) Kiglapait mineralogy III: olivine compositions and Rayleigh fractionation models. J Petrol 37:1037–1061CrossRefGoogle Scholar
  32. Nakamoto K (1978) Infrared and Raman spectra of inorganic and coordination compounds. Wiley-Interscience, New YorkGoogle Scholar
  33. Navrotsky A (1995) Thermodynamic properties of minerals. In: Ahrens TJ (ed) A handbook of physical constants. American Geophysical Union, Washington, pp 18–28Google Scholar
  34. Pitman KM, Hofmeister AM, Speck AK, Dijkstra C (2007) Room temperature forsterite and fayalite absorbances. Mon Not R Astron Soc (in preparation)Google Scholar
  35. Redfern SAT, Artioli G, Rinaldi R, Henderson CMB, Knight K S, Wood BJ (2000) Octahedral cation ordering in olivine at high temperature. II: An in situ neutrol powder diffraction study on synthetic MgFeSiO4 (Fa50). Phys Chem Mineral 27:630–637CrossRefGoogle Scholar
  36. Reynard B (1991) Single-crystal infrared reflectivity of pure Mg2SiO4 forsterite and (Mg0.86,Fe0.14)2SiO4 olivine—new data and a reappraisal. Phys Chem Mineral 18:19–25Google Scholar
  37. Rinaldi R, Artioli G, Wilson CC, McIntyre G (2000) Octaheral cation ordering in olivine at high temperature. I: In situ neutron single-cyrstal diffraction studies on natural mantle olivines (Fa12 and Fa10). Phys Chem Mineral 27:623–629CrossRefGoogle Scholar
  38. Robie RA, Hemingway BS, Fisher JR (1978) Thermodynamic properties of minerals and related substances at 298.15 K and 1 bar (105 Pa) and at higher temperatures. US Geol Surv Bull 1452:1–456Google Scholar
  39. Schwab RG, Küstner D (1977) Präzionsgitterkonstantenbestimmung zur Festlegung röntgenographischer Bestimmungkurven für synthetishee Olivine der Mischkristallreihe Forsterit–Fayalit. N J Miner Mh 1977:205–215Google Scholar
  40. Servoin JL, Piriou B (1973) Infrared reflectivity and Raman scattering of Mg2SiO4 single crystal. Phys Status Solid B 55:677–686Google Scholar
  41. Sogawa H, Koike C, Chihara H, Suto H, Tachibana S, Tsuchiyama A, Kozasa T (2006) Infrared reflection spectra of forsterite crystal. Astron Astrophys 451:357–361CrossRefGoogle Scholar
  42. Suto H, Koike C, Sogawa H, Tsuchiyama A, Chihara H, Mizutani K (2002) Infrared spectra of fayalite crystal. Astron Astrophys 389:568–571CrossRefGoogle Scholar
  43. Tarantino SC, Carpenter MA, Domeneghetti MC (2003) Strain and local heterogeneity in the forsterite–fayalite solid solution. Phys Chem Mineral 30:495–502CrossRefGoogle Scholar
  44. 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. Advances in Physical Geochemistry, vol 1. Springer, New York, pp 63–84Google Scholar
  45. Wood BJ, Kleppa OJ (1981) Thermochemistry of forsterite–fayalite olivine solutions. Geochem Cosmochim Acta 45:529–534CrossRefGoogle Scholar
  46. Wooten F (1972) Optical properties of solids. Academic, New York, p 260Google Scholar
  47. Yoder HS Jr, Sahama TG (1957) Olivine X-ray determinative curve. Am Mineral 42:475–491Google Scholar

Copyright information

© Springer-Verlag 2007

Authors and Affiliations

  1. 1.Department of Earth and Planetary SciencesWashington University—St LouisSt LouisUSA

Personalised recommendations