At the nanoscale the positions of coexistence lines on the phase diagrams are shifted and their new locations depend mainly on the size and shape of the nano-confinement, the structure of the confining walls, and their interaction with the confined substance. Here we show that it is possible to induce structural transformations in a confined system by simply varying the number of molecules adsorbed in the pore. We found that the mechanism of these novel, adsorption-induced structural transformation in nano-pores differs from the capillary condensation. First, the structure of the confined gas is determined by a competition between adsorption sites attractive forces and intermolecular interaction. Second, at low temperature, the transformation is discontinuous because it is defined by limited number of adsorption sites [1,2]. The confined, equilibrium structures are not characterized by mean positions of molecules but rather by a probability distribution of molecular positions around adsorption centres. This distribution changes when the number of molecules in the pore increases. The character of transformation is temperature dependent: strongly discontinuous at low temperature, it evolves into a continuous transition when the temperature increases. The mechanism of the transformation is also modified when the size of the gas molecules and types of interaction change. In particular, we report the existence of the intermediate phase, observed only above a critical strength of the attractive interactions. This work was supported by the Polish National Science Centre (NCN, grant no. 2015/17/B/ST8/00099). The calculations have been partially performed at the WCSS computer center of The Wroclaw University of Science and Technology, grant no 33.

At the nanoscale the positions of coexistence lines on the phase diagrams are shifted and their new locations depend mainly on the size and shape of the nano-confinement, the structure of the confining walls, and their interaction with the confined substance. Here we show that it is possible to induce structural transformations in a confined system by simply varying the number of molecules adsorbed in the pore. We found that the mechanism of these novel, adsorption-induced structural transformation in nano-pores differs from the capillary condensation. First, the structure of the confined gas is determined by a competition between adsorption sites attractive forces and intermolecular interaction. Second, at low temperature, the transformation is discontinuous because it is defined by limited number of adsorption sites1,2.The confined, equilibrium structures are not characterized by mean positions of molecules but rather by a probability distribution of molecular positions around adsorption centres. This distribution transforms when the number of molecules in the pore increases. The character of transformation depends on temperature: it is strongly discontinuous at low temperature but evolves into a continuous transition when the temperature increases. Here we show how the mechanism of the transformation is modified by temperature and also by different types of interaction and the size of the gas molecules. In particular, the existence of the intermediate phase is observed only above a critical strength of the attractive interactions.

Phase changes are ubiquitous in nature, and transformations between solid structures represent a large group of them. They are usually reported on phase diagrams, as coexistence lines between different structures. The phase diagrams, well established for macroscopic 3-dimensional (3D) materials, change drastically when the material’s dimensions are reduced to few nanometers, or if the material is confined in a nano-pore. At the nanoscale the positions of coexistence lines on the phase diagrams are shifted and their new locations depend mainly on the size and shape of the nano-confinement, the structure of the confining walls, and their interaction with the confined substance. Here we show that it is possible to induce structural transformations in a confined system by simply varying the number of molecules adsorbed in the pore. We found that the mechanism of these novel, adsorption-induced structural transformation in nano-pores differs from that of well-known capillary condensation. The confined, equilibrium structures are not characterized by mean positions of molecules but rather by a probability distribution of molecular positions around adsorption centres. The character of transformation depends on temperature: it is strongly discontinuous at low temperature but evolves into a continuous transition when the temperature increases.