Pressure-induced elongation of hydrogen-oxygen bond in sodium silicate melts

Ohashi, Tomonori*; Sakamaki, Tatsuya*; Funakoshi, Kenichi*; Steinle-Neumann, G.*; Hattori, Takanori   ; Yuan, L.*; Suzuki, Akio*

We explore the structures of dry and hydrated (HO and DO) NaSiO melt at 0-6 GPa and 1000-1300 K and glasses recovered from high pressure and temperatures by in-situ neutron and X-ray diffraction. The structures of the melts at 0-10 GPa and 3000 K are also investigated by ab-initio molecular dynamics simulation. In-situ neutron experiments revealed that the D-O distance increases with compression due to the formation of -O-D-O- bridging species, which is reproduced by the molecular dynamics simulations. The pressure-induced -O-D-O- formation reflects a more rigid incorporation of hydrogen, which acts as a mechanism for the experimentally observed higher solubility of water in silicate melts. Together with shrinking modifier domains, this process dominates the compression behavior of hydrous NaSiO melt, whereas the compression of dry NaSiO at 0-10 GPa and 3000 K is governed largely by bending of the Si-O-Si angle. The molecular dynamics simulations on hydrous NaSiO melts further suggest that the sodium ions are scavenged from its network-modifying role via 2(Si-O + Na) Si-(O-Si-O) + 2Na and Si-O + Na + Si-OH Si-(O-H-O-Si) + Na with increasing pressure.