Spin Transitions in Lower Mantle Minerals Concentrate on
- Slides: 34
Spin Transitions in Lower Mantle Minerals? Concentrate on ferropericlase as more likely to have a big effect
Electron configurations • K shell 1 s • L shell 2 s 2 p • M shell 3 s 3 p 3 d • • • s suborbitals take up to 2 electrons p suborbitals take up to 6 electrons d suborbitals take up to 10 electrons • Fe 2+ has 24 electrons, 2 in K, 8 in L and 14 in M with 6 in 3 d
Structure of ferropericlase -- green are oxygen and blue are magnesium or iron
(note eg orbitals point towards nearest neighbor oxygens and t 2 g point between)
Fe(2+): 3 d shell has 6 (out of 8) electrons -- prefer to be unpaired (high spin) Fp Pv Note aluminous Pv can have Fe(3+) as well as Fe(2+) Volume contraction is not as great in Pv because outlying orbitals still populated
Xray emission spectroscopy • • • K-shell electron absorbs an Xray photon and is ejected A 3 p electron collapses into the K-shell The resulting 3 p hole interacts with the partially filled 3 d shell (the interaction is a function of the spin state of the 3 d shell) Main peak is associated with K-beta emission -- satellite peak associated with 3 d shell -- intensity of peak depends on spin polarization of 3 d shell Satellite peak disappears when all 3 d is in low spin state
Fp (0. 17) -- this is expected composition if Fe partitions preferentially into Fp
Lin et al, 2007 (Science -- in press)
Lin et al, 2007 (Science -- in press)
Summary of experimental results • • All experiments at room temperature (except Lin et al 2007) Ferropericlase: transition range at 40 --60 GPa? Large weakening of elastic moduli during transition. Experiments are for Fe rich specimens (Fe#=17 --25) or for Fe#=6 corrected to larger value. LS phase seems more opaque (lower thermal conductivity). There is a clear increase in density between high and low spin states at room temperature. Enough data to estimate an EOS for high spin and low spin states Perovskite: some find two sharp transitions, some a continuous transition over a wide pressure band (likely in aluminous samples). Some find that LS state is more transparent (higher thermal conductivity)? Effect on elasticity may be mininal (but still important? ) Theoretical calculations and experiment at high T suggest broad pressure transition range
Fp (0. 17) (Lin et al, 2005)
Fp (0. 20) (Fei et al 2007)
Some thermodynamics!
Xfe=0. 06 Xfe=0. 17 Crowhurst et al 2008
Xfe=0. 17, T=300 K, no modulus weakening Red is HS and blue is LS; black line prediction of model
Xfe=0. 17, T=300 K, modulus weakening
Xfe=0. 06 Xfe=0. 17 Crowhurst et al 2008
Can use observed width of transition to fix d. E in thermo model at high T Lin et al, 2007 (Science)
Xfe=0. 17, T=1800 K, modulus weakening Red is HS, blue is LS and black is prediction of model
How does this affect fit to lower mantle properties?
Red=density Blue=Vc Green=Vs Xfe=0. 17 Modulus weakening “pyrolite” + spin transition in ferropericlase
Red=density Blue=Vc Green=Vs Xfe=0. 17 No weakening “pyrolite” + spin transition in ferropericlase
Conclusions • • 1 D seismic models are extremely well-known in most of the lower mantle and, along with advances in mineral physics, are useful for constraining the bulk composition of the Earth A limited range of compositions fit the seismic models (though the precision of the mineral physics estimates of shear velocity is a limiting factor) Recent results on the elastic properties of the spin crossover in ferropericlase result in bulk sound speed velocities and velocity gradients in the lower mantle which are apparently incompatible with the 1 D seismic models. Perhaps anomalous elastic effects are diminished at high T? Or perhaps Fe is not so strongly partitioned into ferropericlase (the partitioning may be controlled by the presence of small amounts of aluminum, etc) Partitioning may also be a function of spin state -- just to make life more interesting Don’t need to rewrite all the text books just yet!
Future work • Need high T experimental data on elasticity • Need better data for perovskite since this is the bulk of the lower mantle • Need to look at seismic constraints on velocity gradients since these may be most diagnostic
Fp (0. 25)
Pv (0. 1) -- broad transition?
Aluminous sample -- broad transition
(Crowhurst, Brown, Goncharov and Jabobesen, submitted to Science), uses ISS
(Crowhurst, Brown, Goncharov and Jabobesen, submitted to Science),
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