Water on metal oxides interfaces generate a variety of ordered motifs that depend on the structural properties of the exposed solid surfaces. Here we emphasize the importance of considering the thermodynamic state of the surrounding liquid to find the interface structures in real systems. In particular, using ab-initio molecular dynamics, we have studied the thermodynamic behavior of the water induced reconstructed (WIR) anatase (001) surface under full hydration. The long standing issue of the reconstruction symmetry in this facet of the anatase, that is the TiO₂ stable phase at the nanoscale, is addressed showing that the stable state for a WIR surface in vacuum and in bulk water are different, the latter depending on the thermodynamic state of the system. Thermally activated surface phase transitions between (2x4) and (2x3) symmetries are lead by the surface relaxation caused by the molecular adsorption and release phenomena at the interface. Our approach enables the validation to aqueous environment of surface-confined water structures derived in vacuum, emphasizing the role of the thermodynamics conditions for characterizing solid-liquid interfaces especially for nano sized systems.

金属氧化物界面上的水会产生各种有序的图案，这些图案取决于裸露的固体表面的结构特性。在这里，我们强调考虑周围液体的热力学状态以在实际系统中找到界面结构的重要性。特别地，使用从头开始的分子动力学，我们研究了在完全水合作用下水诱导的重建（WIR）锐钛矿（001）表面的热力学行为。在锐钛矿的这一方面，即TiO ₂，重建对称性的长期存在的问题解决了纳米级的稳定相，表明WIR表面在真空中和在大量水中的稳定状态不同，后者取决于系统的热力学状态。（2x4）和（2x3）对称性之间的热活化表面相变是由界面处的分子吸附和释放现象引起的表面弛豫导致的。我们的方法能够验证在真空中产生的表面受限水结构的水环境，从而强调了热力学条件对表征固液界面（特别是对于纳米级系统）的作用。