Abstract
Crystal field stabilization (CFS) plays a significant role in determining equilibrium phase boundaries in olivine→spinel transformations involving transition-metal cations, including Fe2+ which is a major constituent of the upper mantle. Previous calculations for Fe2SiO4 ignored pressure and temperature dependencies of crystal field stabilization enthalpies (CFSE) and the electronic configurational entropy (S CFS). We have calculated free energy changes (ΔG CFS) due to differences of crystal field splittings between Fe2SiO4 spinel and fayalite from: ΔG CFS=−ΔCFSE−TΔS CFS, as functions of P and T, for different energy splittings of t 2g orbital levels of Fe2+ in spinel. The results indicate that ΔG CFS is always negative, suggesting that CFS always promotes the olivine→spinel transition in Fe2SiO4, and expands the stability field of spinel at the expense of olivine. Because of crystal field effects, transition pressures for olivine→spinel transformations in compositions (Mg1−x Fe x )2SiO4 are lowered by approximately 50x kbar, which is equivalent to having raised the olivine→spinel boundary in the upper mantle by about 15 km.
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Burns, R.G., Sung, CM. The effect of crystal field stabilization on the olivine→spinel transition in the system Mg2SiO4 - Fe2SiO4 . Phys Chem Minerals 2, 349–364 (1978). https://doi.org/10.1007/BF00307577
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DOI: https://doi.org/10.1007/BF00307577