| Summary: | The degree to which the Earth’s mantle stores and cycles water in excess of the storage capacity of nominally anhydrous minerals is dependent upon the stability of hydrous phases under mantle-relevant pressures, temperatures, and compositions. Two hydrous phases, phase D and phase H, are stable to the pressures and temperatures of the Earth’s lower mantle, suggesting that the Earth’s lower mantle may participate in the cycling of water. We build on our prior work of density functional theory calculations on phase H with the stability, structure, and bonding of hydrous phases D, and we predict the aluminum partitioning with H in the Al<inline-formula> <math display="inline"> <semantics> <msub> <mrow></mrow> <mn>2</mn> </msub> </semantics> </math> </inline-formula>O<inline-formula> <math display="inline"> <semantics> <msub> <mrow></mrow> <mn>3</mn> </msub> </semantics> </math> </inline-formula>-SiO<inline-formula> <math display="inline"> <semantics> <msub> <mrow></mrow> <mn>2</mn> </msub> </semantics> </math> </inline-formula>-MgO-H<inline-formula> <math display="inline"> <semantics> <msub> <mrow></mrow> <mn>2</mn> </msub> </semantics> </math> </inline-formula>O system. We address the solid solutions through a statistical sampling of site occupancy and calculation of the partition function from the grand canonical ensemble. We show that each phase has a wide solid solution series between MgSi<inline-formula> <math display="inline"> <semantics> <msub> <mrow></mrow> <mn>2</mn> </msub> </semantics> </math> </inline-formula>O<inline-formula> <math display="inline"> <semantics> <msub> <mrow></mrow> <mn>6</mn> </msub> </semantics> </math> </inline-formula>H<inline-formula> <math display="inline"> <semantics> <msub> <mrow></mrow> <mn>2</mn> </msub> </semantics> </math> </inline-formula>-Al<inline-formula> <math display="inline"> <semantics> <msub> <mrow></mrow> <mn>2</mn> </msub> </semantics> </math> </inline-formula>SiO<inline-formula> <math display="inline"> <semantics> <msub> <mrow></mrow> <mn>6</mn> </msub> </semantics> </math> </inline-formula>H<inline-formula> <math display="inline"> <semantics> <msub> <mrow></mrow> <mn>2</mn> </msub> </semantics> </math> </inline-formula> and MgSiO<inline-formula> <math display="inline"> <semantics> <msub> <mrow></mrow> <mn>4</mn> </msub> </semantics> </math> </inline-formula>H<inline-formula> <math display="inline"> <semantics> <msub> <mrow></mrow> <mn>2</mn> </msub> </semantics> </math> </inline-formula>-2<inline-formula> <math display="inline"> <semantics> <mi>δ</mi> </semantics> </math> </inline-formula>AlOOH + SiO<inline-formula> <math display="inline"> <semantics> <msub> <mrow></mrow> <mn>2</mn> </msub> </semantics> </math> </inline-formula>, in which phase H is more aluminum rich than phase D at a given bulk composition. We predict that the addition of Al to both phases D and H stabilizes each phase to higher temperatures through additional configurational entropy. While we have shown that phase H does not exhibit symmetric hydrogen bonding at high pressure, we report here that phase D undergoes a gradual increase in the number of symmetric H-bonds beginning at ∼30 GPa, and it is only ∼50% complete at 60 GPa.
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