Density functional theory simulations were carried out to study the formation and
migration energetics and geometric structures of the native point defects and
protons in Mg2SiO4 polymorphs (namely,
forsterite, wadsleyite and ringwoodite) up to 30 GPa pressure. The energetic favorability of the vacancy and interstitial
defects was shown to strongly depend on the atomic and electron chemical
potentials. Among the chargebalanced defects studied, the Mg2+-Frenkel defects are energetically most favorable in forsterite whereas the
MgO pseudo-Schottky defects are energetically most favorable in wadsleyite and ringwoodite. Our results
for the ion migration enthalpies calculated using the nudged-elastic-band technique suggest that the Mg
migration is easiest in forsterite and ringwoodite whereas Si migration is easiest in wadsleyite. The proton
incorporations at the interstitial and vacant cationic sites were investigated. In the extrinsic limit, the proton
incorporation is energetically most favorable at VSi'''' site for up to three protons.
Addition of one more proton prefers to go to VMg''' site. In the intrinsic limit,
however, the interstitial and Mg-vacancy sites remain the most favorable. The
predicted barrier for the interstitial-to-interstitial proton migration is smaller than
that for the magnesium vacancy-to-interstitial migration, and among three phases ringwoodite has the lowest barrier.
The effects of proton incorporation on the transition pressure and pressure–volume equation of state were
shown to be significant.
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