RESEARCH LETTER
10.1029/2019GL083472
Key Points:
• The dissociation phase boundary of
phase H MgSiO4 H2 is determined by
calculation of Gibbs free energy of ice
VII
• Phase H decomposes into MgSiO3
bridgmanite and H2 O ice VII at
approximately 60 GPa
• The transportation of water by
DHMSs may be terminated at a depth
of approximately 1,500-km depth in a
pure Mg-endmember composition
Correspondence to:
J. Tsuchiya,
junt@ehime-u.ac.jp
Citation:
Tsuchiya, J., & Umemoto, K. (2019).
First-principles determination of the
dissociation phase boundary of phase
H MgSiO4 H2 . Geophysical Research
Letters, 46, 7333–7336. https://doi.org/
10.1029/2019GL083472
Received 25 APR 2019
Accepted 3 JUN 2019
Accepted article online 11 JUN 2019
Published online 8 JUL 2019
©2019. American Geophysical Union.
All Rights Reserved.
TSUCHIYA AND UMEMOTO
First-Principles Determination of the Dissociation Phase
Boundary of Phase H MgSiO4 H2
Jun Tsuchiya1,2 and Koichiro Umemoto2
1 Geodynamics Research Center, Ehime University, Matsuyama, Ehime, Japan, 2 Earth-Life Science Institute, Tokyo
Institute of Technology, Japan
Abstract Phase H (MgSiO4 H2 ) is considered an important carrier of water into the lower mantle by the
subduction of slabs. This phase has been reported to decompose into H2 O ice VII and MgSiO3 bridgmanite
under pressure. However, the dissociation phase boundary under the mantle pressure and temperature
conditions has not been determined thus far. In this work, the dissociation phase boundary of phase H is
determined by the calculation of Gibbs free energy of H2 O ice VII. The stability field of phase H is found to
be significantly extended from 52 to 62 GPa by the inclusion of zero-point vibrational energy. Phase H
decomposes into MgSiO3 bridgmanite and H2 O ice VII at approximately 60 GPa (at ∼1000 K). This result
indicates that the transportation of water by dense hydrous magnesium silicates may be terminated at a
depth of approximately 1,500 km in the middle of the lower mantle in a pure Mg-endmember composition.
1. Introduction
The determination of stability fields of the hydrous phases under the mantle pressure and temperature con-
ditions is the key to understanding the circulation of water in the Earth's deep interior. In recent years,
several theoretical and experimental investigations on hydrous phases have been conducted extensively in
order to explore the carrier and reservoir of water in the deeper part of the Earth's interior. It is generally
assumed that water is transported into the Earth's interior by dense hydrous magnesium silicates (DHMSs)
in subducting cold slabs (Ohtani et al., 2001; Ringwood & Major, 1967; Schmidt & Poli, 1998). The existence
of the new DHMS under lower mantle pressure conditions has been predicted by first-principles calcu-
lation (Tsuchiya, 2013), subsequently identified by the high-pressure experiment, and named as phase H
MgSiO4 H2 (Nishi et al., 2014).
Tsuchiya (2013) reported that phase D (MgSi2 O6 H2 ) transforms into phase H and SiO2 stishovite above
∼40 GPa. The phase boundary between phase D and phase H plus SiO2 has been determined by the calcula-
tion of Gibbs free energy based on quasiharmonic approximation (QHA) and density functional perturbation
theory (DFPT). The Clapeyron slope dP∕dT = ΔS∕ΔV of the phase boundary at 1000 K is positive at approx-
imately ∼6.4 MPa/K. This discovery of a new phase further extends the stability field of DHMSs toward
higher pressure. Tsuchiya (2013) also suggests that phase H decomposes into MgSiO3 bridgmanite and H2 O
above 52 GPa under the static 0-K condition. The dissociation phase boundary of phase H under finite tem-
perature conditions was not determined, since it was difficult to calculate the Gibbs free energy of H2 O for
high-temperature conditions.
H2 O has a very rich phase diagram (e.g., Bartels-Rausch et al., 2012). Under higher-pressure conditions
(above ∼2 GPa), ice VII, VIII, and X are identified, experimentally. Low-temperature phase ice VIII is stable
below approximately 270 K, whereas ice VII is stabilized under higher-temperature conditions. Both ice VII
and VIII consist of two interpenetrating diamond-type oxygen sublattices. Ice VII is hydrogen-disordered
and body-centered cubic, while ice VIII is hydrogen-ordered and body-centered tetragonal. Under the man-
tle pressure and temperature conditions that we are interested in, ice VII is the thermodynamically stable
phase. In order to calculate the Gibbs free energy of the ice VII phase, we need to calculate not only the
vibrational entropy but also the configurational entropy due to the disordered hydrogen positions.
If the subducting slab transports water as a form of MgSiO4 H2 phase H into greater depths, the dissociation
reaction of phase H into MgSiO3 bridgmanite and H2 O ice VII is expected (Nishi et al., 2014; Tsuchiya, 2013).
Here we calculated the Gibbs free energy of ice VII using the partition function of ice VII to determine the
dissociation phase boundary of phase H.
7333
 Geophysical Research Letters 10.1029/2019GL083472

Figure 1. Lowest-energy hydrogen configurations in the 16 H2 O supercells, their degeneracies Wi (i = 1 ∼ 52), and the
enthalpy differences from ice VIII at 0 GPa. Large and small spheres indicate oxygen and hydrogen atoms, respectively.

2. Methods
Umemoto et al. (2010) successfully calculated the phase boundary of order-disorder phase transition
between ice VII and VIII based on DFPT and QHA. Here we follow the same method to calculate the Gibbs
free energy of ice VII. The calculation of ice VII was modeled using a supercell (2 ×2× 2 unit cells) con-
taining 16 H2 O molecules. This supercell has 90 × 90 = 8,100 possible hydrogen configurations, satisfying
the ice rule (Pauling, 1935). However, the number of hydrogen configurations can be reduced to 52 after
considering symmetry (Figure 1). Within QHA, the partition function of this system is

∑
52
∑
∞
1 ∑1 144
ZQHA (V, T) = Wi exp{− (E (V) + ℏ𝜔 (V))}
i=1 ns,i=0
kB T i s=1
2 s,i

1 ∑
144
· exp(− n ℏ𝜔 )
kB T s=1 s,i s,i
∑
52
1 ∑1 144
= Wi exp{− (Ei (V) + ℏ𝜔 (V))}
i=1
kB T s=1
2 s,i
∏
144
ℏ𝜔s,i (V)
· {1 − exp(− )},
s=4
kB T

where kB is Boltzmann's constant, Ei (V) and Wi are the total energy and degeneracy of the ith symmetrically
∑52
inequivalent configuration ( i=1 Wi = 8, 100), and 𝜔s,i (V) and ns,i are the sth phonon frequency and the
corresponding number of excited phonons, respectively, for the ith configuration. Using the partition func-
tion ZQHA , the Helmholtz (F) and Gibbs (G) free energies are given by, F = −kB T ln ZQHA and G = F + PV,
respectively.
The first-principles calculation is based on the density functional theory with the generalized gradient
approximation to the exchange-correlation functional(Perdew et al., 1996). Norm-conserving pseudopoten-
tials (Troullier & Martins, 1991) were used and extensively tested in previous studies (e.g., Tsuchiya, 2013;
Tsuchiya & Tsuchiya, 2009a, 2009b). All structural parameters are fully relaxed at static 0 K at 0, 10, 20, 30,
40, 50, 60, 80, 100, and 120 GPa using damped variable cell shape molecular dynamics implemented with
Quantum ESPRESSO codes (Giannozzi et al., 2009). In this study, 144 phonon frequencies of the ice super-
cell are calculated based on DFPT (Baroni et al., 2001). The zone-center phonon mode (Γ point) is sampled
for the calculation of the partition function ZQHA .
For the determination of the dissociation phase boundary, we used the Gibbs free energy of phase H, and
MgSiO3 perovskite determined based on DFPT and QHA (Tsuchiya, 2013).

3. Results and Discussions

Figure 2 shows the phase diagram of the phase H (MgSiO4 H2 ) composition. The previous static 0-K calcula-
tion (Tsuchiya, 2013) indicates that phase H decomposes into MgSiO3 bridgmanite and H2 O above 52 GPa.
In the present study, we have determined the dissociation phase boundary of phase H (MgSiO4 H2 ) into
H2 O ice VII and MgSiO3 under the finite temperature condition using QHA, as shown by the thick red line.
The dissociation of phase H occurs above 60 GPa even for the 0-K condition. The inclusion of zero-point
vibration energy notably increased the stability of phase H. This is presumably because the hydrogen bond

TSUCHIYA AND UMEMOTO 7334

 Geophysical Research Letters 10.1029/2019GL083472

symmetrization of phase H occurs at 30 GPa and 0 K, which is signif-

icantly lower than that of ice (approximately 100 GPa under static 0-K
conditions) and the summation of zero-point vibration in equation (1) is
eventually smaller than for dissociation products.
Several experimental studies reported the existence of phase H up to
around 60 GPa (Nishi et al., 2018; Ohtani et al., 2014; Walter et al., 2015).
However, it is usually difficult to determine precise thermodynamic
phase boundaries by experiments, as the transition is often restricted
at low temperature because sufficient thermal energy required for the
reaction to proceed is unavailable. However, our theoretical phase bound-
ary of phase H is more consistent with recent experiments compared
to the tentative phase boundary determined by static 0-K calculation
(Tsuchiya, 2013). Therefore, the present results suggest that phase H is
stable around 60 GPa, especially under low-temperature conditions, and
these experimental findings in those conditions are not caused by such
kinetic effects.
The calculated free energy difference between VII and VIII is approxi-
mately 0.02 and 0.05 eV/H2 O at 300 and 1000 K, respectively. If we use
free energy of ice VIII for the determination of the dissociation bound-
ary, the dissociation pressure of phase H is about 5 GPa higher than the
present study at 1000 K. Although the present result indicates that the
Figure 2. Calculated high-pressure dissociation phase boundary from Gibbs free energy of ice VII determined by QHA can be used for the
MgSiO4 H2 phase H to MgSiO3 bridgmanite and H2 O ice VII (heavy red determination of the dissociation phase boundary, the hydrogen behav-
line). The gray symbols and lines are phase boundaries of high-pressure ice
ior of ice under high pressure and temperature condition is considered
(Dubrovinskaia & Dubrovinsky, 2003; Goncharov et al., 2005; Kimura et al.,
2014; Millot et al., 2018; Redmer et al., 2011; Schwager et al., 2004; more complicated. The superionic phase, which has liquid-like behavior
Schwager & Boehler, 2008; Schwegler et al., 2008). The cold geotherm is of hydrogen, whereas the oxygen lattice is maintained, has been theo-
estimated about 500 K lower than the adiabatic mantle geotherm (Brown & retically predicted above approximately 1000 K (Cavazzoni et al., 1999)
Shankland, 1981). and was recently identified by the shock compression experiment (Mil-
lot et al., 2018). In addition, we have only considered the static hydrogen
positions. However, under high-pressure conditions above ∼50 GPa near the phase boundary between ice
VII and X, the dynamically disordered hydrogen phase has been reported (Caracas, 2008; Sugimura et al.,
2010) by the thermal vibration and quantum tunneling effects (Benoit et al., 1998). These effects should be
included for more accurate determination of the free energy of ice phases.
The present result indicates that the dissociation phase boundary of phase H intersects with the cold
geotherm around 60 GPa. Figure 2 shows that the several previous melting temperatures of ice are higher
than that of the cold geotherm under lower mantle pressure conditions (Millot et al., 2018; Redmer et al.,
2011; Schwager & Boehler, 2008; Schwager et al., 2004, 2008). Therefore, there is a possibility that the dis-
sociation of phase H produces the superionic ice phase in the middle of the lower mantle at a depth of
Acknowledgments
The research was supported in part by around 1,500 km. The crystal chemical reactions between superionic ice and surrounding minerals have not
Grants-In-Aid for Scientific Research been understood yet. However, the high diffusivity of hydrogen in superionic ice may presumably produce
from the Japan Society for the a reaction faster than that in solid ice but slower than that in water, that is, the liquid phase of H2 O (Bina &
Promotion of Science (Grants
15H05834 for J. T. and 17K05627 for Navrotsky, 2000).
K. U.). This research was also
supported by MEXT as “Exploratory
Finally, the real mantle is a multicomponent system, and the effects of impurities, such as Fe and Al, should
Challenge on Post-K computer” be taken into account. Recent experiments and theoretical calculations have also revealed the phase relations
(Challenge of Basic Science-Exploring between phase H and other hydrous phases such as 𝛿 -AlOOH (Nishi et al., 2014; Ohira et al., 2014; Panero
Extremes through Multi-Physics and
Multi-Scale Simulations). We are
& Caracas, 2017) and FeOOH (Nishi et al., 2017). These phase relations should be understood based on the
grateful to Craig Bina and an revised phase diagram reported in this study.
anomymous reviewer who helped to
improve the manuscript. The data used
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