Behavior of hydrogarnet-type defects in hydrous stishovite at various
temperatures and pressures
Abstract
Dense polymorphs of silica have been demonstrated experimentally to
incorporate from 1.5% to as much as 11.6% weight percent
H2O as OH groups, with implications for the hydrogen
budgets of Earth and other planets. This OH is thought to enter the
SiO2 structure via a charge-balanced substitution in
which silicon vacancies (VSi) are compensated by
protonating four of the surrounding six oxygen atoms, often referred to
as a hydrogarnet-type defect. There are many possible configurations for
this defect structure in dense silica, but the nature of these
configurations and whether they can be distinguished experimentally is
unknown. We present here density functional theory (DFT) calculations
that systematically assess the possible configurations of a
hydrogarnet-type defect in stishovite (rutile-type
SiO2), with direct comparisons to experimental
vibrational spectroscopy data. We predict that stishovite synthesized at
450 K and 10 GPa quenched to room temperature is dominated by a single
defect type with tetrahedral geometry. This leads to OH stretching modes
(2500-3000 cm-1) and SiOH bending modes
(~1400 to 1450 cm-1) largely
consistent with experimentally observed modes. One remaining issue is
that our calculations produce results compatible with experimental data
on H to D exchange, but do not explain why a considerable fraction of
the 1420 cm-1 mode shifts by only 40
cm-1 in deuterated samples. At elevated pressures and
temperatures, we find that a second square planar defect configuration
also becomes favorable, leading to modes that should allow
differentiation from the tetrahedral configuration.