Intrinsic Oxygen Vacancy and Extrinsic Aluminium Dopant Interplay: A Route to the Restoration of Defective TiO2_2

Density functional theory (DFT) and DFT corrected for on-site Coulomb interactions (DFT+U) calculations are presented on Aluminium doping in bulk TiO$_2$ and the anatase (101) surface. Particular attention is paid to the mobility of oxygen vacancies throughout the doped TiO$_2$ lattice, as a means by which charge compensation of trivalent dopants can occur. The effect that Al doping of TiO$_2$ electrodes has in dye sensitised solar cells is explained as a result of this mobility and charge compensation. Substitutional defects in which one Al3+ replaces one Ti4+ are found to introduce valence band holes, while intrinsic oxygen vacancies are found to introduce states in the band-gap. Coupling two of these substitutional defects with an oxygen vacancy results in exothermic defect formation which maintain charge neutrality. Nudged elastic band calculations have been performed to investigate the formation of these clustered defects in the (101) surface by oxygen vacancy diffusion, with the resulting potential energy surface suggesting energetic gains with small diffusion barriers. Efficiency in- creases observed in dye sensitised solar cells as a result of aluminium doping of TiO$_2$ electrodes are investigated by adsorbing the tetrahydroquinoline C2-1 chromophore on the defective surfaces. Adsorption on the clustered extrinsic Al3+ and intrinsic oxygen vacancy defects are found to behave as if adsorbed on a clean surface, with vacancy states not present, while adsorption on the oxygen vacancy results in a down shift of the dye localised states within the band-gap and defect states being present below the conduction band edge. Aluminium doping therefore acts as a benign dopant for 'cleaning' TiO$_2$ through oxygen vacancy diffusion.Comment: 32 pages, 15 figures, accepted for publication by J. Phys. Chem.

DSSC Anchoring Groups: A Surface Dependent Decision

Electrodes in dye sensitised solar cells (DSSCs) are typically nanocrystalline anatase TiO2 with a majority (101) surface exposed. Generally the sensitising dye employs a carboxylic anchoring moiety through which it adheres to the TiO2 surface. Recent interest in exploiting the properties of differing TiO2 electrode morphologies, such as rutile nanorods exposing the (110) surface and anatase electrodes with high percentages of the (001) surface exposed, begs the question of whether this anchoring strategy is best, irrespective of the majority surface exposed. Here we address this question by presenting density functional theory calculations contrasting the binding properties of two promising anchoring groups, phosphonic acid and boronic acid, to that of carboxylic acid. Anchor-electrode interactions are studied for the pro- totypical anatase (101) surface, along with the anatase (001) and rutile (110) surfaces. Finally the effect of using these alternative anchoring groups to bind a typical coumarin dye (NKX- 2311) to these TiO2 substrates is examined. Significant differences in the binding properties are found depending on both the anchor and surface, illustrating that the choice of anchor is necessarily dependent upon the surface exposed in the electrode. In particular the boronic acid is found to show the potential to be an excellent anchor choice for electrodes exposing the anatase (001) surface.Comment: 44 pages, 15 figures, accepted by J. Phys.:Condens. Matter. Coordinates for structures available via figshar

Linear Scaling Density Matrix Real Time TDDFT: Propagator Unitarity \& Matrix Truncation

Real time, density matrix based, time dependent density functional theory proceeds through the propagation of the density matrix, as opposed to the Kohn-Sham orbitals. It is possible to reduce the computational workload by imposing spatial cut-off radii on sparse matrices, and the propagation of the density matrix in this manner provides direct access to the optical response of very large systems, which would be otherwise impractical to obtain using the standard formulations of TDDFT. Following a brief summary of our implementation, along with several benchmark tests illustrating the validity of the method, we present an exploration of the factors affecting the accuracy of the approach. In particular we investigate the effect of basis set size and matrix truncation, the key approximation used in achieving linear scaling, on the propagator unitarity and optical spectra. Finally we illustrate that, with an appropriate density matrix truncation range applied, the computational load scales linearly with the system size and discuss the limitations of the approach.Comment: Accepted for publication in J. Chem. Phy

EFFICACY OF ELECTRON BEAM IRRADIATION OF PROCESSED PORK PRODUCTS

The research reported on in this paper was conducted as part of a larger project. That project is on-going and is focused on ascertaining if irradiation of processed meats would be effective and economical. It involved the examination, through modeling, of the irradiation of one of many currently produced ready-to-eat (RTE) convenience-oriented, value-added pork products, sliced boneless ham. The results and findings reported in this paper represent the initial estimates of the cost and potential profitability or economic viability of irradiation of processed meats. The results and findings in this paper should be considered preliminary with extension and verification to be reported in a later paper by the authors. The objective of the portion of that project reported on in this paper was to conduct cost analysis of alternative irradiation methods and to ascertain the cost of each of those methods. Three scenarios were considered for cost analysis. The first scenario was the installation of an X-ray irradiator at an existing meat processing plant. The second scenario was the installation of a Cobalt-60 irradiator at an existing meat processing plant. The third scenario assumed that the meat processor contracted for irradiation services from an off-site company providing such service to a number of clients. For purposes of this study it was assumed that irradiation of sliced boneless ham would result in either a $.06/pound reduction in costs from processor to consumer, a$.06/pound increase in willingness to pay [price] or an equivalent combination of reduced costs and increased price. Total cost per pound for the irradiation process applied to sliced boneless ham ranged from $0.008, at the 200 million pound annual throughput rate using Cobalt-60 irradiation, to$0.069 at the 50 million pound annual throughput rate when contracting with an off-site company.Food Consumption/Nutrition/Food Safety,

Globalization, growth and distribution in Spain 1500-1913

The endogenous growth literature has explored the transition from a Malthusian world where real wages, living standards and labor productivity are all linked to factor endowments, to one where (endogenous) productivity change embedded in modern industrial growth breaks that link. Recently, economic historians have presented evidence from England showing that the dramatic reversal in distributional trends – from a steep secular fall in wage-land rent ratios before 1800 to a steep secular rise thereafter – must be explained both by industrial revolutionary growth forces and by global forces that opened up the English economy to international trade. This paper explores whether and how the relationship was different for Spain, a country which had relatively poor productivity growth in agriculture and low living standards prior to 1800, was a late-comer to industrialization afterwards, and adopted very restrictive policies towards imports for much of the 19th century. The failure of Spanish wagerental ratios to undergo a sustained rise after 1840 can be attributed to the delayed fall in relative agricultural prices (due to those protective policies) and to the decline in Spanish manufacturing productivity after 1898