Visualization-based analysis of structural and dynamical properties of simulated hydrous silicate melt |
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Authors: | Bijaya B Karki Dipesh Bhattarai Mainak Mookherjee Lars Stixrude |
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Institution: | 1. Department of Computer Science, Louisiana State University, Baton Rouge, LA, 70803, USA 2. Department of Geology and Geophysics, Louisiana State University, Baton Rouge, LA, 70803, USA 3. Bayerisches Geoinstitut, Universit?t Bayreuth, Bayreuth, 95440, Germany 4. Department of Earth Sciences, University College London, London, WC1E 6BT, UK
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Abstract: | We have explored first-principles molecular dynamics simulation data for hydrous MgSiO3 liquid (with 10 wt% water) to gain insight into its structural and dynamical behavior as a function of pressure (0–150 GPa)
and temperature (2,000–6,000 K). By visualizing/analyzing a number of parameters associated with short- and mid-range orders,
we have shown that the melt structure changes substantially on compression. The speciation of the water component at low pressures
is dominated by the isolated structures (with over 90% hydrogen participated) consisting of hydroxyls, water molecules, O–H–O
bridging and four-atom (O–H–O–H and H–O–H–O) groups, where every oxygen atom may be a part of polyhedron or free (i.e., bound
to only magnesium atom). Hydroxyls favor polyhedral sites over magnesium sites whereas molecular water is almost entirely
bound to magnesium sites, and also interpolyhedral bridging (Si–O–H–O–Si) dominates other types of bridging. Water content
is shown to enhance and suppress, respectively, the proportions of hydroxyls and molecular water. As compression increases,
these isolated structures increasingly combine with each other to form extended structures involving a total of five or more
O and H atoms and also containing threefold coordination species, which together consume over 80% hydrogen at the highest
compression studied. Our results show that water lowers the mean coordination numbers of different types including all cation–anion
environments. The hydrous melt tends to be more tetrahedrally coordinated but with the Si–Si network being more disrupted
compared to the anhydrous melt. Protons increase the content of non-bridging oxygen and decrease the contents of bridging
oxygen as well as oxygen triclusters (present at pressures above 10 GPa). The calculated self-diffusion coefficients of all
atomic species are enhanced in the presence of water compared to those of the anhydrous melt. This is consistent with the
prediction that water depolymerizes the melt structure at all pressures. Our analysis also suggests that proton diffusion
involves two processes—the transfer of H atoms (requiring the rupture and formation of O–H bonds) and the motion of hydroxyls
as hydrogen carriers (requiring the rupture and formation of Si–O and/or Mg–O bonds). Both the processes are operative at
low compression whereas only the first process is operative at high compression. |
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