Changes of structure and dipole moment of water with temperature and pressure: a first principles study

The changes of structure and distribution of dipole moment of water with temperatures up to 2800 K and densities up to 2.2 g/cm(3) are investigated using ab initio molecular dynamics. Along the isochore of 1.0 g/cm(3), the structure of liquid water above 800 K is dramatically different from that at ambient conditions, where the hydrogen-bonds network collapses. Along the isotherm of 1800 K, the transition from the liquid state to an amorphous superionic phase occurs at 2.0 g/cm(3) (32.9 GPa), which is not observed along the isotherm of 2800 K. With increasing temperature, the average dipole moment of water molecules is decreased arising from the weakened polarization by the collapse of the hydrogen-bonds network, while it is contrarily increased with compression due to the strengthening effect upon the polarization of water molecules. Both higher temperature and pressure broaden the distribution of dipole moment of water molecules due to the enhanced intramolecular charge fluctuations.