Exoteric effects at nanoscopic interfaces - Uncommon negative compressibility of nanoporous materials and unexpected cavitation at liquid/liquid interfaces

This PhD thesis is devoted to the investigation of some peculiar effects happening at nanoscopic interfaces between immiscible liquids or liquids and solids via molecular dynamics simulations. The study of the properties of interfaces at a nanoscopic scale is driven by the promise of many interesting technological applications, including: a novel technology for developing both eco-friendly energy storage devices in the form of mechanical batteries, as well as energy dissipation systems and, in particular, shock absorbers for the automotive market; biomedical applications related to cavitation, such as High-Intensity Focused Ultrasound (HIFU) ablation of cancer tissues and localised drug delivery, and many more. The kinetics of phenomena taking places at these scales is typically determined by large free-energy barriers separating the initial and final states, and even intermediate metastable states, when they are present. Because of such barriers, the phenomena we are interested in are "rare events", i.e. the system attempts the crossing of the barrier(s) many times before finally succeeding when an energy fluctuation makes it possible. At the same time, the magnitude of the barrier is determined by the energetics and dynamics of atoms, which forces us to model the system by taking into account both the femtosecond atomistic timescale and the timescale of the relevant phenomena, typically exceeding the former by several orders of magnitude. These longer timescales are inaccessible to standard molecular dynamics, so, in order to tackle this issue, advanced MD techniques need to be employed. The thesis is divided into two parts, corresponding to the main lines of research investigated, which are (I) the interfaces between water and complex nanoporous solids, and (II) planar solid-liquid and liquid-liquid interfaces. Anticipating some results, atomistic simulations helped uncovering the microscopic mechanism behind the (incredibly rare!) giant negative compressibility exhibited by the ZIF-8 metal organic framework (MOF) upon water intrusion. Molecular dynamics simulations also supported experimental results showing how it is possible to change the intermediate intrusion-extrusion performance of ZIF-8 by changing its grain morphology and arrangement, from a fine powder to compact monolith. Free-energy MD calculations allowed to explain the exceptional stability of surface nanobubbles in water, at undersaturated conditions, on a surprisingly wide variety of substrates, characterized by disparate hydrophobicities and gas affinities; and yet, how they catastrophically destabilize in organic solvents. Finally, through simulations, some light was shed upon the working mechanism behind the novelly discovered phenomenon of how the interface between two immiscible liquids can act as a nucleation site for cavitation.