Optical absorption spectra of ferropericlase to 84 GPa

被引:66
作者
Keppler, Hans [1 ]
Kantor, Innokenty [1 ]
Dubrovinsky, Leonid S. [1 ]
机构
[1] Univ Bayreuth, Bayer Geoinst, D-95440 Bayreuth, Germany
关键词
ferropericlase; spin-pairing; low-spin; iron; optical spectra; radiative conductivity; crystal field splitting; Racah parameter; Jahn-Teller effect;
D O I
10.2138/am.2007.2454
中图分类号
P3 [地球物理学]; P59 [地球化学];
学科分类号
0708 ; 070902 ;
摘要
Optical and near infrared absorption spectra of ferropericlase Mg0.88Fe0.12O have been measured to 84 GPa. Under ambient conditions, the spectrum shows two crystal field bands of high-spin Fe 21 at 8922 and 12533 cm(-1), which shift to higher frequencies with increasing pressure (dv/dP = 50.7 and 85.5 cm(-1)/GPa). Simultaneously, the intensity of the high-frequency band continuously decreases until it vanishes around 40 GPa, suggesting a quenching of the Jahn-Teller effect. Between 51 and 60 GPa, the absorption spectrum changes drastically. Two new bands appear at 60 GPa at 9728 and 14592 cm(-1) with frequency shifts at higher pressures of dv/dP = 23.8 and 21.0 cm(-1)/GPa, respectively. If the change in optical spectra between 51 and 60 GPa were interpreted as being due to spin-pairing, the crystal field parameters of low-spin Fe2+ at 60 GPa would be Delta = 10 546 cm(-1) and B = 377 cm(-1). This would imply that the main cause of spin-pairing is not the increase in crystal field splitting Delta, but the stronger covalency of the Fe-O bond as seen in the reduction of the Racah parameter B. Even at 84 GPa, ferropericlase is by no means opaque. In particular, the inferred spin-pairing transition between 51 and 60 GPa reduces radiative thermal conductivity only by about 15%. Spin-pairing in ferropericlase is therefore unlikely to have major consequences for the temperature distribution or the mode of convection in the lower mantle. The absorption edge of the high-pressure phase appears to be deeper in the UV than for the low-pressure phase, which could imply a reduced electrical (polaron) conductivity.
引用
收藏
页码:433 / 436
页数:4
相关论文
共 16 条
  • [1] Thermochemical state of the lower mantle: New insights from mineral physics
    Badro, J
    Fiquet, G
    Guyot, F
    [J]. EARTH'S DEEP MANTLE: STRUCTURE, COMPOSITION, AND EVOLUTION, 2005, 160 : 241 - 260
  • [2] Iron partitioning in Earth's mantle:: Toward a deep lower mantle discontinuity
    Badro, J
    Fiquet, G
    Guyot, F
    Rueff, JP
    Struzhkin, VV
    Vankó, G
    Monaco, G
    [J]. SCIENCE, 2003, 300 (5620) : 789 - 791
  • [3] Pressure dependence of H solubility in magnesiowustite up to 25 GPa: Implications for the storage of water in the Earth's lower mantle
    Bolfan-Casanova, N
    Mackwell, S
    Keppler, H
    McCammon, C
    Rubie, DC
    [J]. GEOPHYSICAL RESEARCH LETTERS, 2002, 29 (10) : 89 - 1
  • [4] Burns R.G., 1993, Mineralogical Applications of Crystal Field Theory, V5
  • [5] CLARK SP, 1957, T AM GEOPHYS UNION, V38, P931
  • [6] Figgis B. N., 1966, INTRO LIGAND FIELDS
  • [7] Reduced radiative conductivity of low-spin (Mg,Fe)O in the lower mantle
    Goncharov, Alexander F.
    Struzhkin, Viktor V.
    Jacobsen, Steven D.
    [J]. SCIENCE, 2006, 312 (5777) : 1205 - 1208
  • [8] THEORY OF HIGH-SPIN REVERSIBLE LOW-SPIN TRANSITIONS IN TRANSITION-METAL COMPOUNDS INDUCED BY THE JAHN-TELLER EFFECT
    KAMBARA, T
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1979, 70 (09) : 4199 - 4206
  • [9] Spin crossover in (Mg,Fe)O: A Mossbauer effect study with an alternative interpretation of x-ray emission spectroscopy data
    Kantor, IY
    Dubrovinsky, LS
    McCammon, CA
    [J]. PHYSICAL REVIEW B, 2006, 73 (10)
  • [10] Optical and near infrared spectra of ringwoodite to 21.5 GPa: Implications for radiative heat transport in the mantle
    Keppler, H
    Smyth, JR
    [J]. AMERICAN MINERALOGIST, 2005, 90 (07) : 1209 - 1212