To Wet or Not to Wet? Dispersion Forces Tip the Balance for Water Ice on Metals

Despite widespread discussion, the role of van der Waals dispersion forces in wetting remains unclear. Here we show that nonlocal correlations contribute substantially to the water-metal bond and that this is an important factor in governing the relative stabilities of wetting layers and 3D bulk ice. Because of the greater polarizability of the substrate metal atoms, nonlocal correlations between water and the metal exceed those between water molecules within ice. This sheds light on a long-standing problem, wherein common density functional theory exchange-correlation functionals incorrectly predict that none of the low temperature experimentally characterized icelike wetting layers are thermodynamically stable

Advanced CO2 removal process control and monitor instrumentation development

A progam to evaluate, design and demonstrate major advances in control and monitor instrumentation was undertaken. A carbon dioxide removal process, one whose maturity level makes it a prime candidate for early flight demonstration was investigated. The instrumentation design incorporates features which are compatible with anticipated flight requirements. Current electronics technology and projected advances are included. In addition, the program established commonality of components for all advanced life support subsystems. It was concluded from the studies and design activities conducted under this program that the next generation of instrumentation will be greatly smaller than the prior one. Not only physical size but weight, power and heat rejection requirements were reduced in the range of 80 to 85% from the former level of research and development instrumentation. Using a microprocessor based computer, a standard computer bus structure and nonvolatile memory, improved fabrication techniques and aerospace packaging this instrumentation will greatly enhance overall reliability and total system availability

Trends in water monomer adsorption and dissociation on flat insulating surfaces

The interaction of water with solid surfaces is key to a wide variety of industrial and natural processes. However, the basic principles that dictate how stable and in which state (intact or dissociated) water will be on a given surface are not fully understood. Towards this end, we have used density functional theory to examine water monomer adsorption on the (001) surfaces of a broad range of alkaline earth oxides, alkaline earth sulfides, alkali fluorides, and alkali chlorides. Some interesting general conclusions are arrived at: (i) on all the surfaces considered only a few specific adsorption structures are favoured; (ii) water becomes more stable upon descending the oxide and fluoride series but does not vary much upon going down the chloride and sulfide series; (iii) water is stabilised both by an increase in the lattice constant, which facilitates hydrogen bonding to the substrate, and by the flexibility of the substrate. These are also factors that favour water dissociation. We hope that this study is of some value in better understanding the surface science of water in general, and in assisting in the interpretation and design of future experiments

Towards an accurate theoretical description of surface processes

Molecular modelling methods are indispensable for both helping to understand experimental results and to explore new materials. In this thesis we focus on theoretical methods that are used to study activated processes at surfaces as well as those which can account for van der Waals dispersion forces. To begin, we examine existing methods and develop a few new ones that are suitable for identifying transition states in chemical reactions. We discuss in detail how the various methods compare in efficiency for some simple chemical processes on an NaCl surface (water diffusion and HCl dissociation). The interaction of water with salt is then extended, focussing on the interaction of water clusters (up to 20 water molecules) with clean and defected salt surfaces. The aim of this part of the thesis is to understand in detail the initial stages of NaCl dissolution. In the remainder of the thesis we focus on a problem suffered by many current density functional theory methods, namely their inability to accurately account for dispersion forces. We test a recently proposed non-local functional and show how its accuracy can be dramatically improved with some simple modifications. The new functional(s) are tested on a wide variety of materials and highly encouraging results have been obtained