High-pressure studies of ammonia hydrates
Wilson, Craig W.
Ammonia and water are major components of many planetary bodies, from comets and icy moons such as Saturn's Titan to the interiors of the planets Neptune and Uranus. Under a range of high pressures and/or low temperatures known to occur in these planetary bodies, ammonia and water form a series of compounds known as ammonia hydrates. Ammonia and water form three stoichiometric compounds, ammonia hemihydrate, ammonia monohydrate and ammonia dihydrate, which have ammonia-to-water ratios of 2:1, 1:1 and 1:2 respectively. Therefore a good understanding of the three stable ammonia hydrates is required for modelling the interiors of these bodies. Additionally, the ammonia hydrates are the simplest systems to incorporate mixed (N-H O and O-H N) hydrogen bonds. Such bonds are important biochemically, and along with O-H O H-bonds, mixed H-bonds are responsible for the second-order structure of DNA, and they are also responsible for the proton transfer reactions in enzymic processes. The understanding of these bonds and processes rests on the knowledge of the relationship between bond strength and geometry, and the ammonia hydrates provide a rich range of geometries against which models of such mixed H-bonds can be tested. X-ray and neutron diffraction techniques have been used to investigate the behaviour of the ammonia-water complex and further the understanding of this system. This includes solving the structure of a phase which was previously thought to be an ammonia monohydrate phase, but has been shown here to be a mixture of an ammonia hemihydrate phase and Ice VII. In addition to this, x-ray and neutron diffraction experiments have been performed to explore how this phase behaves under changing pressure and temperature conditions, and what other implications that this has on the ammonia-water system. It has been found that ammonia hemihydrate can also form a structural phase observed to form in both ammonia monohydrate and ammonia dihydrate within the same pressure and temperature regime, which opens the possibility of a solid solution existing between all three stoichiometric ammonia hydrates.