Nucleation of Capillary Bridges and Bubbles in Nanoconfined CO2.

Using molecular simulation, we examine the capillary condensation and the capillary evaporation of CO2 in cylindrical nanopores. More specifically, we employ the recently developed μV T-S method to determine the microscopic mechanism associated with these processes and the corresponding free energy profiles. We calculate the free energy barrier for capillary condensation and identify that the key step consists in the nucleation of a liquid bridge of a critical size. Similarly, the free energy maximum found for the capillary evaporation process is found to correspond to the nucleation of a vapor bubble of a critical size. In addition, we assess the impact of the strength of the wall-fluid on the height of the free energy barrier and on the critical size of liquid bridges (condensation process) and vapor bubbles (evaporation process). We observe that the height of the free energy barrier increases with the strength of the wall-fluid interactions. Finally, we build a theoretical model, based on capillary theory, to rationalize our findings. In particular, the simulation results reveal a linear scaling of the free energy barrier with the critical size, in excellent agreement with the theoretical predictions.