Local Structure of Hydrogen-Bonded Liquids

Ordinary yet unique, water is the substance on which life is based. Water seems, at first sight, to be a very simple molecule, consisting of two hydrogen atoms attached to one oxygen. Its small size belies the complexity of its action and its numerous anomalies, central to a broad class of important phenomena, ranging from global current circulation, terrestrial water and CO2 cycles to corrosion and wetting. The explanation of this complex behavior comes from water's unique ability to form extensive three-dimensional networks of hydrogen-bonds, whose nature and structures, in spite of a great deal of efforts involving a plethora of experimental and theoretical techniques, still lacks a complete scientific understanding. This thesis is devoted to the study of the local structure of hydrogen-bonded liquids, with a particular emphasis on water, taking advantage of a combination of core-level spectroscopies and density functional theory spectra calculations. X-ray absorption, in particular, is found to be sensitive to the local hydrogen-bond environment, thus offering a very promising tool for spectroscopic identification of specific structural configurations in water, alcohols and aqueous solutions. More specifically, the characteristic spectroscopic signature of the broken hydrogen-bond at the hydrogen side is used to analyze the structure of bulk water, leading to the finding that most molecules are arranged in two hydrogen-bond configurations, in contrast to the picture provided by molecular dynamics simulations. At the liquid-vapor interface, an interplay of surface sensitive measurements and theoretical calculations enables us to distinguish a new interfacial species in equilibrium with the gas. In a similar approach the cluster form of the excess proton in highly concentrated acid solutions and the different coordination of methanol at the vacuum interface and in the bulk can also be clearly identified. Finally the ability of core-level spectroscopies, aided by sophisticated density functional theory calculations, to directly probe the valence electronic structure of a system is used to observe the nature of the interaction between water molecules and solvated ions in solution. Water around transition metal ions is found to interact with the solute via orbital mixing with the metal d-orbitals. The hydrogen-bond between water molecules is explained in terms of electrostatic interactions enhanced by charge rehybridization in which charge transfer between connecting molecules is shown to be fundamental.

Towards Automation in Digital Investigations : Seeking Efficiency in Digital Forensics in Mobile and Cloud Environments

Cybercrime and related malicious activity in our increasingly digital world has become more prevalent and sophisticated, evading traditional security mechanisms. Digital forensics has been proposed to help investigate, understand and eventually mitigate such attacks. The practice of digital forensics, however, is still fraught with various challenges. Some of the most prominent of these challenges include the increasing amounts of data and the diversity of digital evidence sources appearing in digital investigations. Mobile devices and cloud infrastructures are an interesting specimen, as they inherently exhibit these challenging circumstances and are becoming more prevalent in digital investigations today. Additionally they embody further characteristics such as large volumes of data from multiple sources, dynamic sharing of resources, limited individual device capabilities and the presence of sensitive data. These combined set of circumstances make digital investigations in mobile and cloud environments particularly challenging. This is not aided by the fact that digital forensics today still involves manual, time consuming tasks within the processes of identifying evidence, performing evidence acquisition and correlating multiple diverse sources of evidence in the analysis phase. Furthermore, industry standard tools developed are largely evidence-oriented, have limited support for evidence integration and only automate certain precursory tasks, such as indexing and text searching. In this study, efficiency, in the form of reducing the time and human labour effort expended, is sought after in digital investigations in highly networked environments through the automation of certain activities in the digital forensic process. To this end requirements are outlined and an architecture designed for an automated system that performs digital forensics in highly networked mobile and cloud environments. Part of the remote evidence acquisition activity of this architecture is built and tested on several mobile devices in terms of speed and reliability. A method for integrating multiple diverse evidence sources in an automated manner, supporting correlation and automated reasoning is developed and tested. Finally the proposed architecture is reviewed and enhancements proposed in order to further automate the architecture by introducing decentralization particularly within the storage and processing functionality. This decentralization also improves machine to machine communication supporting several digital investigation processes enabled by the architecture through harnessing the properties of various peer-to-peer overlays. Remote evidence acquisition helps to improve the efficiency (time and effort involved) in digital investigations by removing the need for proximity to the evidence. Experiments show that a single TCP connection client-server paradigm does not offer the required scalability and reliability for remote evidence acquisition and that a multi-TCP connection paradigm is required. The automated integration, correlation and reasoning on multiple diverse evidence sources demonstrated in the experiments improves speed and reduces the human effort needed in the analysis phase by removing the need for time-consuming manual correlation. Finally, informed by published scientific literature, the proposed enhancements for further decentralizing the Live Evidence Information Aggregator (LEIA) architecture offer a platform for increased machine-to-machine communication thereby enabling automation and reducing the need for manual human intervention.