Water inside a nanocapillary exhibits unconventional structural and dynamical behavior due to its ordered structure. The confining walls, density, and lateral pressures control profoundly the microscopic structure of trapped water. Here we study the electrostriction of confined water subjected to pressures of the order of GPa for two different setups: (i) a graphene nanochannel containing a constant number of water molecules independent of the height of the channel, (ii) an open nanochannel where water molecules can be exchanged with those in a reservoir. For the former case, a square-rhombic structure of confined water is formed when the height of the channel is $d=6.5$ Å having a density of $\rho =1.42{\mathrm{g}\mathrm{cm}}^{-3}$. By increasing the height of the channel, a transition from a flat to a buckled state occurs, whereas the density rapidly decreases and reaches the bulk density for $d\cong 8.5$ Å. When a perpendicular electric field is applied, the water structure and the lateral pressure change. For strong electric fields $(\sim 1$ V/Å), the square-rhombic structure is destroyed. For an open setup, a solid phase of confined water consisting of an imperfect square-rhombic structure is formed. By applying a perpendicular field, the density and phase of confined water change. However, the density and pressure inside the channel decrease as compared to the first setup. Our study is closely related to recent experiments on confined water, and it reveals the sensitivity of the microscopic structure of confined water to the size of the channel, the external electric field, and the experimental setup.

• Received 23 October 2017

DOI:https://doi.org/10.1103/PhysRevB.97.144111