Computer simulations of liquids with intrinsic microporosity

Designing porous materials capable of hosting molecular species in cavities of molecular dimensions is an important goal in materials science and engineering. Contrary to the small, transient cavities that exist in the interstitial voids between the molecules of any conventional liquid, a "porous liquid" possesses well-defined, permanent voids inherent to the molecular architecture of the liquid molecules. The efficacy of such a microporous liquid lies in the ability of these intramolecular cavities to selectively house molecular guests. In this thesis we use computer simulations to embark on the first investigation into the microporous nature of potential "porous liquids", and establish whether this novel concept is viable. Simulations studies, using models as an approximation to the geometry of cage-like molecules, suggest that it is possible to design a system that exhibits permanent microporosity in the liquid phase. By calculating the distribution of cavity sizes in the liquid samples and simulating gas absorption experiments, we also establish that an existing system (synthesised by our experimental collaborators) is a potential candidate as the first microporous liquid.EThOS - Electronic Theses Online ServiceGBUnited Kingdo