Platinum Group Metals and Their Oxides in Semiconductor Photosensitisation BASIC PRINCIPLES, METAL PHOTODEPOSITION AND WATER PHOTOSPLITTING REACTIONS

The basic principles of semiconductor photochemistry, particularly using titania as a semiconductor photocatalyst, are discussed. When a platinum group metal or its oxide is deposited onto the surface of a sensitised semiconductor the overall efficiency of the reactions it takes part in are often improved, especially when the deposits are used as hydrogen and oxygen catalysts, respectively. Methods of depositing metal or metal oxide are examined, and a particular focus is given to a photodeposition process that uses a sacrificial electron donor. Platinum group metal and platinum group metal oxide coated semiconductor photocatalysts are prominent in heterogeneous systems that are capable of the photoreduction, oxidation and cleavage of water. There is a recent renaissance in work on water-splitting semiconductor-sensitised photosystems, but there are continued concerns over their irreproducibility, longevity and photosynthetic nature.

Annotated Bibliography: Grande Bretagne / Great Britain: Part Three: The Problem of Rights and the Literature of Constitutional Reform

(With C.N. Doe.)

Allometric analysis of Sitka spruce branches:Mechanical versus hydraulic design principles

The geometry of tree branches can have considerable effect on their efficiency in terms of carbon export per unit carbon investment in structure. The purpose of this study was to evaluate different design criteria using data describing the form of Picea sitchensis branches. Allometric analysis of the data suggests that resources are distributed to favour shoots with the greatest opportunity for extension into new space, with priority to the extension of the leader. The distribution of allometric relations of links (branch elements) was tested against two models: the pipe model, based on hydraulic transport requirements, and a static load model based on the requirement of shoots to provide mechanical resistance to static loads. Static load resistance required the load parameter to be proportional to the link radius raised to the power of 4. This was shown to be true within a 95% statistical confidence limit. The pipe model would require total distal length to be proportional to link radius squared but the measured branches did not conform well to this model. The comparison suggests that the diameters of branch elements were more related to the requirements for mechanical load. The cost of following a hydraulic design principle (the pipe model) in terms of mechanical efficiency was estimated and suggested that the pipe model branch would not be mechanically compromised but would use structural resources inefficiently. Resource allocation among branch elements was found to be consistent with mechanical stability criteria but also indicated the possibility of allocation based on other criteria, such as potential light interception by shoots. The evidence suggests that whilst branch topology increments by reiteration of units of morphogenesis, the geometry follows a functional design pattern.

Statistical-mechanical description of classical test-particle dynamics in the presence of an external force field: modelling noise and damping from first principles

Aiming to establish a rigorous link between macroscopic random motion (described e.g. by Langevin-type theories) and microscopic dynamics, we have undertaken a kinetic-theoretical study of the dynamics of a classical test-particle weakly coupled to a large heat-bath in thermal equilibrium. Both subsystems are subject to an external force field. From the (time-non-local) generalized master equation a Fokker-Planck-type equation follows as a "quasi-Markovian" approximation. The kinetic operator thus defined is shown to be ill-defined; in specific, it does not preserve the positivity of the test-particle distribution function f(x, v; t). Adopting an alternative approach, previously introduced for quantum open systems, is proposed to lead to a correct kinetic operator, which yields all the expected properties. A set of explicit expressions for the diffusion and drift coefficients are obtained, allowing for modelling macroscopic diffusion and dynamical friction phenomena, in terms of an external field and intrinsic physical parameters.